Organic compounds

ABSTRACT

An aryl-substituted alkanal compound having a molecular weight of less than 300 g/mol and which bears a substituent on the aryl ring ortho to a substituent bearing the aldehyde functionality. Said compounds are useful as perfume ingredients in personal care and household care products.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.14/888,887, having a 371(c) date of Nov. 3, 2015, which is a nationalstage application of International Application No. PCT/EP2014/059446,filed 8 May 2014, which claims priority from Great Britain PatentApplication No. 1308236.7, filed 8 May 2013, which applications areincorporated herein by reference.

This invention relates to perfume ingredients and perfume preparationscontaining same. In particular, the invention relates to said perfumeingredients or perfume preparations that exhibit muguet (lily of thevalley) odour characteristics. Still more particularly, the inventionrelates to said perfume preparations that contain no, or substantiallyno, Lilial™. The invention further relates to methods of making saidperfume ingredients and perfume preparations, as well as the use of saidperfume ingredients and perfume preparations in fine fragrances andconsumer products, such as personal care and household care products.The invention also relates to said fine fragrances and consumer productscontaining said perfume ingredients or perfume preparations.

Compounds having muguet odour characteristics are very sought afterperfume ingredients. These compounds are important ingredients in floralbases and can act as harmonizers across many different types offragrance creations. Compounds of this type are used widely in consumerproducts, such as personal care and consumer care products, as well asin fine perfumery, to generate pleasant odours or to mask unpleasantodours.

An excellent perfume ingredient widely valued for its muguet odour noteis Lilial™. Lilial™ is an example of an aryl-substituted alkanal, moreparticularly an aryl-substituted propanal. Specifically, its chemicalname is 3-(4-tert-butylphenyl)-2-methylpropanal (CAS 80-54-6). Thiscompound has found wide use in fine perfumery as well as in personal andhousehold care products. However, its use has come under regulatoryscrutiny in view of recent findings that it exhibits toxic effects onthe reproductive organs of male rats and dogs. No effects were found instudies with mice, guinea-pigs and primates, nevertheless, under theGlobal Harmonized System (GHS) classification system this compound isclassified as a CMR2 material. For CMR category 2 materials, it isnecessary to establish that quantities proposed for use are harmless toconsumers. In view of the regulatory situation of Lilial™ there is aneed to replace it with other perfume ingredients.

WO2010105 873 addresses the problem of replacing Lilial™. The proposedsolution resides in the use of mixtures of known ingredients commonlyfound in the perfumery palette in order to recreate odourcharacteristics substantially similar to those of Lilial™.

Likewise, WO2009027957 proposes a solution residing in the formulationof combinations of known perfume ingredients from the perfumery palette.

WO2013045301 also propose a solution to Lilial™ replacement, whichresides in the selection of mixtures of ingredients including thecompound Lilyflore™ and a certain indanyl propanal compound, incombination with other secondary perfuming ingredients.

The applicant has now found compounds that can be employed as perfumeingredients in perfume compositions and consumer products. Moreparticularly, the applicant has found compounds that possess desirablemuguet odour characteristics. Still more particularly, the applicant hasfound compounds that possess odour characteristics, which may beperceived and recognised by perfumers as being very reminiscent of theodour of Lilial™ and so can serve as a simple replacement for Lilial™.Furthermore, the compounds may have similar or even improved perfumeperformance compared with Lilial™. Finally, the applicant has foundcompounds that do not attract the regulatory concerns associated withLilial™. In particular, the applicant has found that aryl-substitutedalkanal perfume ingredients that are close structural analogues toLilial™ but which, critically, contain a substituent on the aryl ring,which is positioned ortho to the group bearing the aldehydefunctionality, have similar odour characteristics as Lilial™, butsurprisingly carry with them none of the CMR-related issues associatedwith Lilial™ as indicated by in vitro data.

Accordingly, the invention provides in a first aspect anaryl-substituted alkanal compound having a molecular weight of less than300 g/mol and which bears a substituent on the aryl ring ortho to asubstituent bearing the aldehyde functionality, wherein said compound isnot 5-(tert-butyl)-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-(tert-butyl)-2,3-dihydro-1H-indene-2-carbaldehyde,5-isopropyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-isopropyl-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-ethyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-ethyl-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,2,5-dimethyl-2,3-dihydro-1H-indene-2-carbaldehyde,3-(5-(tert-butyl)-2-methylphenyl)propanal,3-(5-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(5-isopropyl-2-methylphenyl)propanal,3-(5-isopropyl-2-methylphenyl)-2-methylpropanal,3-(5-ethyl-2-methylphenyl)propanal,3-(5-ethyl-2-methylphenyl)-2-methylpropanal,3-(4-(tert-butyl)-2-methylphenyl)propanal,3-(4-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(4-isopropyl-2-methylphenyl)propanal,3-(4-isopropyl-2-methylphenyl)-2-methylpropanal,3-(4-ethyl-2-methylphenyl)propanal,3-(4-ethyl-2-methylphenyl)-2-methylpropanal or any of the compounds offormula 3 set forth hereinbelow in which each of R₁ through R₅ is H ormethyl.

In a particular embodiment compounds of the present invention arerepresented by the formula

wherein

R₁, R₂, R₃, R₆ and R₇ each independently may represent H or methyl;

R₄ is H, or when R₅ is H, R₄ is a C₁-C₇ branched or linear, saturated orunsaturated unsubstituted or substituted, optionally with cyclopropylgroups, alkyl residue;

R₅ is H, or when R₄ is H, R₅ is a C₁-C₇ branched or linear, saturated orunsaturated, unsubstituted or substituted, optionally with cyclopropylgroups, alkyl residue; or

R₄ and R₅ together with the carbon atoms to which they are attached,form a substituted or unsubstituted 5-membered ring;

n=0, 1, 2;

the dotted line represents an optional single bond, with the provisothat when the dotted line represents a single bond R₄ or R₅ aresec-butyl, iso-butyl or a C₅-C₇ branched or linear, saturated orunsaturated alkyl residue; and wherein the compounds are not selectedfrom 5-(tert-butyl)-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-(tert-butyl)-2,3-dihydro-1H-indene-2-carbaldehyde,5-isopropyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-isopropyl-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-ethyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-ethyl-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,2,5-dimethyl-2,3-dihydro-1H-indene-2-carbaldehyde,3-(5-(tert-butyl)-2-methylphenyl)propanal,3-(5-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(5-isopropyl-2-methylphenyl)propanal,3-(5-isopropyl-2-methylphenyl)-2-methylpropanal,3-(5-ethyl-2-methylphenyl)propanal,3-(5-ethyl-2-methylphenyl)-2-methylpropanal,3-(4-(tert-butyl)-2-methylphenyl)propanal,3-(4-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(4-isopropyl-2-methylphenyl)propanal,3-(4-isopropyl-2-methylphenyl)-2-methylpropanal,3-(4-ethyl-2-methylphenyl)propanal,3-(4-ethyl-2-methylphenyl)-2-methylpropanal or any of the compounds offormula 3 set forth hereinbelow in which each of R₁ through R₅ is H ormethyl.

In another particular embodiment compounds of the present invention arerepresented by the formula

wherein

R₁, R₂, R₃, and R₆ each independently may represent H or methyl;

R₄ is H, or when R₅ is H, R₄ is a C₁-C₇ branched or linear, saturated orunsaturated unsubstituted or substituted, optionally with cyclopropylgroups, alkyl residue;

R₅ is H, or when R₄ is H, R₅ is a C₁-C₇ branched or linear, saturated orunsaturated, unsubstituted or substituted, optionally with cyclopropylgroups, alkyl residue; or

R₄ and R₅ together with the carbon atoms to which they are attached,form a substituted or unsubstituted 5-membered ring; and wherein thecompounds are not 3-(5-(tert-butyl)-2-methylphenyl)propanal,3-(5-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(5-isopropyl-2-methylphenyl)propanal,3-(5-isopropyl-2-methylphenyl)-2-methylpropanal,3-(5-ethyl-2-methylphenyl)propanal,3-(5-ethyl-2-methylphenyl)-2-methylpropanal,3-(4-(tert-butyl)-2-methylphenyl)propanal,3-(4-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(4-isopropyl-2-methylphenyl)propanal,3-(4-isopropyl-2-methylphenyl)-2-methylpropanal,3-(4-ethyl-2-methylphenyl)propanal,3-(4-ethyl-2-methylphenyl)-2-methylpropanal or any of the compounds offormula 3 set forth hereinbelow in which each of R₁ through R₅ is H ormethyl.

In yet another embodiment of the present invention there is provided acompound according to the formula

wherein

R₁, R₂, and R₃ each independently may represent H or methyl;

R₄ is H, or when R₅ is H, R₄ is an iso-butyl, sec-butyl or linear,saturated or unsaturated, unsubstituted or substituted (optionally withcyclopropyl groups) C₅-C₇ alkyl or alkenyl residue; and

R₅ is H, or when R₄ is H, R₅ is an iso-butyl, sec-butyl or linear,saturated or unsaturated, unsubstituted or substituted (optionally withcyclopropyl groups) C₅-C₇ alkyl or alkenyl residue; and wherein thecompounds are not 3-(5-(tert-butyl)-2-methylphenyl)propanal,3-(5-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(5-isopropyl-2-methylphenyl)propanal,3-(5-isopropyl-2-methylphenyl)-2-methylpropanal,3-(5-ethyl-2-methylphenyl)propanal,3-(5-ethyl-2-methylphenyl)-2-methylpropanal,3-(4-(tert-butyl)-2-methylphenyl)propanal,3-(4-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(4-isopropyl-2-methylphenyl)propanal,3-(4-isopropyl-2-methylphenyl)-2-methylpropanal,3-(4-ethyl-2-methylphenyl)propanal,3-(4-ethyl-2-methylphenyl)-2-methylpropanal or any of the compounds offormula 3 set forth hereinbelow in which each of R₁ through R₅ is H ormethyl.

In yet another particular aspect of the present invention there isprovided a compound of the formula

wherein

R₁ and R₂, each independently may represent H or methyl; and

R₄ represents an iso-butyl or sec-butyl group, or a saturated orunsaturated C₅-C₇ alkyl or alkenyl residue, which may be unsubstitutedor substituted, optionally with cyclopropyl groups.

In yet another particular embodiment of the present invention there isprovided a compound of the formula

wherein

R₁, R₂, and R₃ each independently may represent H or methyl; and

R₅ is a an iso-butyl or sec-butyl group, or a saturated or unsaturatedC₅-C₇ alkyl or alkenyl residue, which may be unsubstituted orsubstituted, optionally with cyclopropyl groups.

In yet another aspect of the present invention there is provided acompound of the formula

Particularly compounds of the present invention include3-(4-isobutyl-2-methylphenyl)propanal,3-(4-isobutyl-2,6-dimethylphenyl)propanal,3-(4-isobutyl-2-3-(4-isobutyl-2-methylphenyl)butanal,3-(4-(sec-butyl)-2-methylphenyl)propanal,3-(2-methyl-4-(tert-pentyl)phenyl)propanal,3-(4-isopentyl-2-methylphenyl)propanal,3-(2-methyl-4-(4-methylpentyl)phenyl)propanal,3-(2-methyl-5-(4-methylpentyl)phenyl)propanal,3-(5-isopentyl-2-methylphenyl)propanal,3-(5-isopentyl-2-methylphenyl)-2-methylpropanal,3-(5-isobutyl-2-methylphenyl)-2-methylpropanal,2-methyl-3-(2-methyl-5-(4-methylpentyl)phenyl)propanal,3-(5-isobutyl-2-methylphenyl)propanal,3-(2-methyl-4-(2-methylbutyl)phenyl)propanal,5-isobutyl-2,3-dihydro-1H-indene-2-carbaldehyde,3-(1,1,6-trimethyl-2,3-dihydro-1H-inden-5-yl)propanal,3-(2-methyl-5-(4-methylpentyl)phenyl)propanal,3-(5-isopentyl-2-methylphenyl)propanal,3-(5-isopentyl-2-methylphenyl)-2-methylpropanal,3-(5-isobutyl-2-methylphenyl)-2-methylpropanal,2-methyl-3-(2-methyl-5-(4-methylpentyl)phenyl)propanal,3-(5-Isobutyl-2-methylphenyl)propanal,3-(4-Isobutyl-2-methylphenyl)propanal,3-(4-isobutyl-2,6-dimethylphenyl)propanal,3-(4-isobutyl-2-methylphenyl)-2-methylpropanal,3-(4-isobutyl-2-methylphenyl)butanal,3-(4-(sec-butyl)-2-methylphenyl)propanal,3-(2-methyl-4-(tert-pentyl)phenyl)propanal,3-(4-isopentyl-2-methylphenyl)propanal and3-(2-methyl-4-(4-methylpentyl)phenyl)propanal.

The compounds of the present invention possess substantially similarodour characteristics and performance characteristics as Lilial™. Assuch, and in contradistinction to the prior art proposals related toLilial™ replacement based on mixtures of known ingredients, the presentinvention can achieve Lilial™ replacement based on a single compound.This has the obvious advantage of representing a cost-effective solutionto the replacement problem, but it is also makes the perfumers' creativeprocess simpler.

Furthermore, compounds of the present invention can generateparticularly substantive and long-lasting muguet odour characteristics.

The compounds of the present invention are particularly impactfulperfume ingredients. The impact that a perfume ingredient exerts isrelated to its Odour Value. Odour Value is the ratio of vapour pressureto detection threshold concentration.

The compounds have extremely high Odour Values. For example, thecompound

has an Odour Value of 559,071. Related perfume ingredients are notimpactful by comparison. For example Lilial™ has an odour value of only32,978 whereas cyclamen aldehyde has an Odour Value of only 21,986.

The remarkably high Odour Value of the compounds of the presentinvention is significant in that there is a need for sustainability andthe provision of impactful perfume ingredients enables perfumers tocreate desirable fragrance accords with lower concentrations ofmaterials.

The regulatory issues surrounding Lilial™ are born from the fact that itis enzymatically degraded in rats and dogs to tert-butyl benzoic acid(t-BBA), which is known to inhibit glucose synthesis and fatty acidsynthesis in vitro (McCune et al, Arch Biochem Biophys (1982) 214 (1):124-133).

tert-Butyl benzoic acid is known to cause testicular effects in malerats (Hunter et so al. Food Cosmet. Toxicol. 1965, 3: 289-298; Cagen etal. J. Am. Coll. Toxicol. 1989, 8 (5): 1027-1038).

In contrast, the compounds of the present invention are not susceptibleto enzyme-mediated degradation to corresponding benzoic acid derivativesin vitro. This was indeed a very surprising result considering theirclose structural similarity to Lilial™.

The applicant's surprising discovery that aryl-substituted alkanalperfume ingredients substituted on the ring at a position ortho to thegroup bearing the aldehyde functionality are not converted to theircorresponding benzoic acid derivatives, provides an insight notheretofore appreciated in the art, which enables perfumers to employ aclass of compounds that although being structurally similar to Lilial™(and therefore possessing remarkably similar olfactive properties asthese compounds), nevertheless do not raise regulatory issues.

In order to study in vitro metabolism in rat hepatocytes, Lilial™ andcompounds of the present invention may be incubated in the presence ofrat hepatocytes in suspension. Reduction in the concentration of Lilial™and the compounds of the present invention and formation of any of thecorresponding benzoic acid derivatives may be analysed by GC-MS.

In another aspect of the present invention there is provided a compoundas herein above defined, which after incubation with hepatocytesisolated from rats, is substantially free of its corresponding benzoicacid degradation product. By “substantially free” is meant that if it ispresent it is below levels of detection, e.g. less than 1%, moreparticularly less than 1% to 0%. As such, compounds of the presentinvention provide perfumers with an eminently suitable surrogate for thevaluable yet problematic Lilial™.

Accordingly, the invention provides in another of its aspects the use ofa compound defined hereinabove as a perfume ingredient.

The invention provides in another of its aspects the use of a compounddefined hereinabove in a perfume composition as a replacement foraryl-substituted alkanal odourants, more particularly aryl-substitutedpropanal odourants, which are unsubstituted on the aryl ring at aposition ortho to the substituent bearing the aldehyde functionality, inparticular Lilial™.

In another aspect of the invention there is provide a method ofimparting a muguet odour characteristic to a perfume composition, saidmethod comprising the step of incorporating a compound definedhereinabove into said perfume composition.

In yet another aspect of the invention there is provided a perfumecomposition comprising a compound defined hereinabove.

In yet another aspect of the invention there is provided a perfumecomposition possessing muguet odour characteristics comprising acompound defined hereinabove.

In yet another aspect of the present invention there is provided aperfume composition comprising a compound defined hereinabove that isfree of any aryl-substituted alkanal odourants, more particularlyaryl-substituted propanal odourants, which are unsubstituted on the arylring at a position ortho to the substituent bearing the aldehydefunctionality, in particular Lilial™.

A perfume composition according to the present invention can be made upentirely by one or more of the compounds of the present invention.However, a perfume composition may also contain, in addition to one ormore of the compounds of present invention, one or more additionalperfume ingredients.

Compounds of the present invention may be present in a perfumecomposition in any amount depending on the particular olfactive effectthat a perfumer wishes to achieve. In a particular embodiment of thepresent invention, a perfume composition of the present invention maycontain compounds defined hereinabove in an amount of 0.1 to 100% byweight of said composition.

If one or more additional perfume ingredients are employed, they may beselected from perfume ingredients known in the art.

In particular, said perfume ingredients that may be employed in aperfume composition according to the invention include6-methoxy-2,6-dimethylheptan-1-al (methoxymelonal),5,9-dimethyl-4,8-decadienal (geraldehyde),beta-methyl-3-(1-methylethyl)benzenepropanal (Florhydral),octahydro-8,8-dimethylnaphthalene-2-carbaldehyde (Cyclomyral),alpha-methyl-1,3-benzodioxole-5-propionaldehyde (helional),5-methyl-2-(1-methylbutyl)-5-propyl-1,3-dioxan (Troenan),3-(o-ethylphenyl)-2,2-dimethylpropionaldehyde (Floralozone), farnesol,3,7,11-trimethyldodeca-1,6,10-trien-3-ol, optionally as an isomericmixture (nerolidol), 2-methyl-4-phenylbutan-2-ol(dimethylphenylethylcarbinol), cis-4-(isopropyl)cyclohexanemethanol(Mayol), 1-(1-hydroxyethyl)-4-(1-methylethyl)cyclohexane (optionally asa mixture of the diastereoisomers) (mugetanol),(4-methyl-3-pentenyl)cyclohexenecarbaldehyde (Citrusal), cyclohexylsalicylate, hexyl salicylate, benzyl salicylate, amyl salicylate,3-(p-(2-methylpropyl)phenyl)-2-methylpropionaldehyde (Silvial),3-p-cumenyl-2-methylpropionaldehyde (cyclamenaldehyde), mixtures of:cis-tetrahydro-2-isobutyl-4-methylpyran-4-ol;trans-tetrahydro-2-isobutyl-4-methylpyran-4-ol; (Florol), triethylcitrate and dipropylene glycol.

Said perfume ingredients may additionally include Amyl Salicylate(2050-08-0); Aurantiol® (89-43-0); Benzyl Salicylate (118-58-1);Cis-3-hexenyl Salicylate (65405-77-8); Citronellyl Oxyacetaldehyde(7492-67-3); Cyclemax (7775-00-0); Cyclohexyl Salicylate (25485-88-5);Cyclomyral® (68738-94-3); Citronellol (106-22-9); Geraniol (106-24-1);Cyclopentol Hc 937165 (84560-00-9); Cymal (103-95-7); Dupical(30168-23-1); Ethyl Linalool (10339-55-6); Floral Super (71077-31-1);Florhydral® (125109-85-5); Florol® (63500-71-0); Gyrane (24237-00-1);Hexyl Salicylate (6259-76-3); Helional™ (1205-17-0); Hydroxycitronellal(107-75-5); Linalool (78-70-6); Lyral® (31906-04-4); Majantol®(103694-68-4); Mayol® (13828-37-0); Melafleur (68991-97-9); Melonal(106-72-9); Mugetanol (63767-86-2); Muguesia (56836-93-2); Muguetalcohol (13351-61-6); Verdantiol (91-51-0); Peonile® (10461-98-0);Phenoxanol® (55066-48-3); Rossitol® (215231-33-7); Silvial® (6658-48-6);Suzural (6658-48-6); Muguol® (18479-57-7); Tetrahydro Linalol (78-69-3);Acalea (84697-09-6); Dihydro Iso Jasmonate (37172-53-5); Hexyl CinnamicAldehyde (101-86-0); Hedione® (24851-98-7); Acetoin (513-86-0); Adoxal(141-13-9); Aldolone® (207228-93-1); Ambrocenide® (211299-54-6);Ambroxan (3738-00-9); Azurone® (362467-67-2); Bacdanol® (28219-61-6);Calone 1951® (28940-11-6); Cetalox® (3738-00-9); Cinnamic alcohol(104-54-1); Citral (5392-40-5); Cyclabute (67634-20-2); Cyclacet™(5413-60-5); Cyclaprop™ (17511-60-3); Cyclohexadecanolide (109-29-5);Cyclohexadecenone (3100-36-5); Cyclopentadecanone (507-72-7); DeltaDamascone (57378-68-4); Ebanol® (67801-20-1); Elintaal Forte(40910-49-4); Ethyl Vanillin (121-32-4); Ethylene Brassylate (105-95-3);Exaltenone 942008 (14595-54-1); Exaltolide Total 935985 (106-02-5);Floral ozone (67634-14-4); Fructalate (72903-27-6); Gamma Decalactone(706-14-9); Habanolide (111879-80-2); Helvetolide® (141773-73-1);Hexamethylindanopyran (1222-05-5); Hydroxyambran® (118562-73-5); Iso ESuper® (54464-57-2); Iso Hexenyl Cyclohexenyl Carboxaldehyde(37677-14-8); Jasmal (18871-14-2); Javanol® (198404-98-7); LauricAldehyde (112-54-9); Mefranal (55066-49-4); Muscenone (63314-79-4);Tonalid® (1506-02-1); Nectaryl® (95962-14-4); Norlim Banol (70788-30-6);Para Hydroxy Phenyl Butanone (5471-51-2); Pino Acetaldehyde(33885-51-7); Romandolide® (236391-76-7); Sanjinol (28219-61-6);Silvanone® Supra (109-29-5/507-72-7); Terpineol (8000-41-7); Vanillin(121-33-5); and Velvione® (37609-25-9), wherein, the figures inparentheses are CAS numbers.

A perfume composition need not be limited to the perfume ingredientslisted above. Other perfume ingredients commonly used in perfumery maybe employed, for example any of those ingredients described in “Perfumeand Flavour Chemicals”, S. Arctander, Allured Publishing Corporation,1994, IL, USA, which is incorporated herein by reference, includingessential oils, plant extracts, absolutes, resinoids, odourants obtainedfrom natural products and the like.

The perfume ingredients contained in said perfume composition aredescribed above, but of course, the perfume composition may not belimited to the stated ingredients. In particular, perfume mixtures maycomprise adjuvants that are commonly employed in perfume formulations.The term “adjuvants” refers to an ingredient that might be employed in aperfume composition for reasons other than, or not specifically, relatedto the composition's olfactive performance. For example, an adjuvant maybe an ingredient that acts as an aid to processing a perfume ingredientor ingredients, or a composition containing said ingredient(s), or itmay improve handling or storage of a perfume ingredient or compositioncontaining same. It might also be an ingredient that provides additionalbenefits such as imparting colour or texture. It might also be aningredient that imparts light resistance or chemical stability to one ormore ingredients contained in a perfume ingredient or compositioncontaining same. A detailed description of the nature and type ofadjuvants commonly used in perfume mixture or compositions containingsame cannot be exhaustive, but it has to be mentioned that saidingredients are well known to a person skilled in the art. Examples ofadjuvants include solvents and co-solvents; surfactants and emulsifiers;viscosity and rheology modifiers; thickening and gelling agents;preservative materials; pigments, dyestuffs and colouring matters;extenders, fillers and reinforcing agents; stabilisers against thedetrimental effects of heat and light, bulking agents, acidulants,buffering agents and antioxidants.

Furthermore, any one or more of the perfume ingredients or adjuvantsemployed in the present invention might be formulated in a deliveryvehicle if desired to provide a desired effect. Delivery vehicles mayinclude encapsulates. Alternatively, a delivery vehicle may be in theform of a solid support, e.g. a polymeric support material onto whichone or more perfume ingredients or adjuvants may be chemically orphysically bound. Still further, one or more perfume ingredients oradjuvants may be dissolved or dispersed in a matrix material, whichserves to control the rate at which said ingredient or ingredientsemanates therefrom. In yet an alternative embodiment, one or moreingredients or adjuvants may be supported on a porous substrate, such asa cyclodextrin or a zeolite or other inorganic material. In a stillfurther embodiment, one or more perfume ingredients may be provided inthe form of a pro-perfume, which will react in a suitable environment torelease the perfume ingredient in a controlled manner.

Having regard to the foregoing, it will be appreciated that a perfumecomposition may be at least partly in solid form, in gel form, in foamform and/or liquid form. If it is present in solid form, it then it maytake the form of granules, powders or tablets.

The present invention provides in another of its aspects a finefragrance or consumer product, such as a personal care or household carecomposition that is perfumed by an aryl-substituted alkanal compoundhaving a molecular weight of less than 300 g/mol and which bears asubstituent on the aryl ring ortho to a substituent bearing the aldehydefunctionality.

In a particular embodiment the invention provides a fine fragrance orconsumer product such as a personal care or household care compositionthat is perfumed by a compound represented by the formula

wherein, R₁, R₂, R₃, R₆ and R₇ each independently may represent H ormethyl;

R₄ is H, or when R₅ is H, R₄ is a C₁-C₇ branched or linear, saturated orunsaturated unsubstituted or substituted, optionally with cyclopropylgroups, alkyl residue;

R₅ is H, or when R₄ is H, R₅ is a C₁-C₇ branched or linear, saturated orunsaturated, unsubstituted or substituted, optionally with cyclopropylgroups, alkyl residue; or

R₄ and R₅ together with the carbon atoms to which they are attached,form a substituted or unsubstituted 5-membered ring;

n=0, 1, 2;

the dotted line represents an optional single bond, with the provisothat when the dotted line represents a single bond R₄ or R₅ aresec-butyl, iso-butyl or a C₅-C₇ branched or linear, saturated orunsaturated alkyl residue.

In another particular embodiment the invention provides a fine fragranceor consumer product, such as a personal care or household carecomposition that is perfumed by a compound represented by the formula

wherein

R₁, R₂, R₃, and R₆ each independently may represent H or methyl;

R₄ is H, or when R₅ is H, R₄ is a C₁-C₇ branched or linear, saturated orunsaturated unsubstituted or substituted, optionally with cyclopropylgroups, alkyl residue;

R₅ is H, or when R₄ is H, R₅ is a C₁-C₇ branched or linear, saturated orunsaturated, unsubstituted or substituted, optionally with cyclopropylgroups, alkyl residue; or

R₄ and R₅ together with the carbon atoms to which they are attached,form a substituted or unsubstituted 5-membered ring.

In another particular embodiment the invention provides a fine fragranceor consumer product, such as a personal care or household carecomposition that is perfumed by a compound represented by the formula

wherein

R₁, R₂, and R₃ each independently may represent H or methyl;

R₄ is H, or when R₅ is H, R₄ is an iso-butyl, sec-butyl or linear,saturated or unsaturated, unsubstituted or substituted (optionally withcyclopropyl groups) C₅-C₇ alkyl or alkenyl residue; and

R₅ is H, or when R₄ is H, R₅ is an iso-butyl, sec-butyl or linear,saturated or unsaturated, unsubstituted or substituted (optionally withcyclopropyl groups) C₅-C₇ alkyl or alkenyl residue.

In another particular embodiment the invention provides a fine fragranceor consumer product, such as a personal care or household carecomposition that is perfumed by a compound represented by the formula

wherein

R₁ and R₂, each independently may represent H or methyl; and

R₄ represents an iso-butyl or sec-butyl group, or a saturated orunsaturated C₅-C₇ alkyl or alkenyl residue, which may be unsubstitutedor substituted, optionally with cyclopropyl groups.

In another particular embodiment the invention provides a fine fragranceor consumer product, such as a personal care or household carecomposition that is perfumed by a compound represented by the formula

wherein

R₁, R₂, and R₃ each independently may represent H or methyl; and

R₅ is an iso-butyl or sec-butyl group, or a saturated or unsaturatedC₅-C₇ alkyl or alkenyl residue, which may be unsubstituted orsubstituted, optionally with cyclopropyl groups.

In another particular embodiment the invention provides a fine fragranceor consumer product, such as a personal care or household carecomposition that is perfumed by a compound represented by the formula

In yet more particular embodiments of the present invention there isprovided a fine fragrance or consumer product, such as a personal careor household care composition that is perfumed by one or more compoundsselected from 3-(4-isobutyl-2-methylphenyl)propanal,3-(4-isobutyl-2,6-dimethylphenyl)propanal,3-(4-isobutyl-2-methylphenyl)-2-methylpropanal,3-(4-isobutyl-2-methylphenyl)butanal,3-(4-(sec-butyl)-2-methylphenyl)propanal,3-(2-methyl-4-(tert-pentyl)phenyl)propanal,3-(4-isopentyl-2-methylphenyl)propanal,3-(2-methyl-4-(4-methylpentyl)phenyl)propanal,3-(2-methyl-5-(4-methylpentyl)phenyl)propanal,3-(5-isopentyl-2-methylphenyl)propanal,3-(5-isopentyl-2-methylphenyl)-2-methylpropanal,3-(5-isobutyl-2-methylphenyl)-2-methylpropanal,2-methyl-3-(2-methyl-5-(4-methylpentyl)phenyl)propanal,3-(5-isobutyl-2-methylphenyl)propanal,3-(2-methyl-4-(2-methylbutyl)phenyl)propanal,5-isobutyl-2,3-dihydro-1H-indene-2-carbaldehyde,3-(4-(tert-butyl)-2-methylphenyl)propanal,3-(4-isopropyl-2-methylphenyl)propanal,3-(1,1,6-trimethyl-2,3-dihydro-1H-inden-5-yl)propanal,3-(2-methyl-5-(4-methylpentyl)phenyl)propanal,3-(5-isopentyl-2-methylphenyl)propanal,3-(5-isopentyl-2-methylphenyl)-2-methylpropanal,3-(5-isobutyl-2-methylphenyl)-2-methylpropanal,2-methyl-3-(2-methyl-5-(4-methylpentyl)phenyl)propanal,3-(5-Isobutyl-2-methylphenyl)propanal,3-(4-isobutyl-2-methylphenyl)propanal,3-(4-isobutyl-2,6-dimethylphenyl)propanal,3-(4-isobutyl-2-methylphenyl)-2-methylpropanal,3-(4-isobutyl-2-methylphenyl)butanal,3-(4-(sec-butyl)-2-methylphenyl)propanal,3-(2-methyl-4-(tert-pentyl)phenyl)propanal,3-(4-isopentyl-2-methylphenyl)propanal and3-(2-methyl-4-(4-methylpentyl)phenyl)propanal.

The compounds defined above, when added to a fine fragrance or consumerproduct, such as a personal care or household care composition, impart acharacteristic muguet odour to said compositions. According to anotheraspect of the present invention there is provided a method of impartingmuguet odour characteristics to a fine fragrance or consumer product,such as a personal care or household care composition comprising thestep of adding to said composition a compound defined above or a perfumecomposition containing said compound.

In yet another aspect of the invention there is provided a method ofimparting muguet odour characteristics to a fine fragrance or consumerproduct, such as a personal care or household care composition,comprising the step of selectively adding to said fine fragrance orconsumer product an aryl-substituted alkanal compound defined above, andselectively excluding from said fine fragrance or consumer product anyaryl-substituted alkanal compounds, which are unsubstituted on the ringat the position ortho to the substituent containing aldehydefunctionality.

In yet another aspect of the invention there is provided a method ofimparting muguet odour characteristics to a fine fragrance or consumerproduct, such as a personal care or household care composition,comprising the step of adding thereto an aryl-substituted alkanalcompound defined above, and selectively excluding from said finefragrance or consumer product any aryl-substituted alkanal compounds,which are unsubstituted on the ring at the position ortho to thesubstituent containing aldehyde functionality, said selective additionor exclusion being based on the susceptibility of said compounds toenzymatically-mediated degradation to their benzoic acid derivativeswhen incubated with hepatocytes isolated from rats, said compounds beingsuitable for addition on the basis that they do not degrade to theirbenzoic acid derivatives under test conditions, whereas said compoundsbeing excluded on the basis that they do degrade to their benzoic acidderivatives under test conditions.

In yet another aspect of the invention there is provided a perfumecomposition comprising an aryl-substituted alkanal compound bearing asubstituent on the aryl ring ortho to a substituent bearing the aldehydefunctionality, in a suitable container, together with labelling thatdoes not contain any CMR2 classification.

Consumer products, such as personal and household care compositionsinclude, but are not limited to a textile treatment product, an ironingaid, a cleaning cloth, a laundry detergent, a cleaning product, inparticular, for hard and/or soft surfaces, a household cleaner, a careproduct, a wash care product, a laundry care product, a room fragrancer,and air freshener, a conditioner, a colorant, a fabric conditioner, aconditioning substrate, a pharmaceutical, a crop protection product, apolish, a food, a cosmetic product, a fertilizer, a building material,an adhesive, a bleach, a decalcifier, an autocare product, floorcareproduct, cookercare product, leathercare product or furniture careproduct, a scourer, a disinfectant, a fragrancer, a mold remover and/ora precursor of the aforementioned products.

The skilled person is fully aware of the applicability of perfumeingredients, and compositions to fine fragrance applications, as well asall manner of consumer product applications, such as personal and household care compositions and a very detailed description of suchcompositions is not warranted here. However, specific compositions thatcan be mentioned include cleaning compositions; autocare compositions;cosmetic compositions; textile treatment compositions; and air freshenerand air care compositions.

Cleaning Products Include:—

Toilet cleaners or lavatory cleaners, in other words, products forcleaning lavatory bowls and urinals, these products being suppliedpreferably in the form of powders, blocks, tablets or liquids,preferably gels. Besides other typical ingredients such as surfactants,they generally include organic acids e.g., citric acid and/or lacticacid) or sodium hydrogen sulfate, amidosulfuric acid or phosphoric acidfor removing limescale or urine scale;

Pipe-cleaning products or drain cleaners. These are typically stronglyalkaline products which serve in general to remove pipe blockagescomprising organic materials-such as hair, fat, food residues, soapdeposits, and the like. Additions of Al powder or Zn powder may servefor the formation of H2 gas with an effervescence effect. Possibleingredients are commonly alkalis, alkaline salts, oxidizing agents, andneutral salts. Supply forms in powder form preferably also includesodium nitrate and sodium chloride. Pipe-cleaning products in liquidform may preferably also include hypochlorite. There are alsoenzyme-based drain cleaners as well. Acidic products are likewisepossible;

Universal or all-purpose or general-purpose cleaners. These are cleanerswhich can be used universally for all hard surfaces in the household andin commerce that can be wiped down wet or damp. Generally speaking, theyare neutral or slightly alkaline or slightly acidic products, especiallyliquid products. All-purpose or general-purpose cleaners generallycontain surfactants, builders, solvents and hydrotropes, dyes,preservatives, and the like;

All-purpose cleaners with special disinfectant properties. Theyadditionally include active antimicrobial ingredients (e.g., aldehydes,alcohols, quaternary ammonium compounds, amphoteric surfactants,triclosan);

Sanitary cleaners. These are products for cleaning in bath and toilet.The alkaline sanitary cleaners are used preferably for removing fattysoiling, whereas the acidic sanitary cleaners are employed inparticular, for removing limescale. Sanitary cleaners advantageouslyalso have a considerable disinfectant action, particularly the stronglyalkaline sanitary cleaners that contain chlorine;

Oven cleaners or grill cleaners which may be supplied in the form ofgels or foam sprays. They generally serve for removing burnt-on orcarbonized food residues. Oven cleaners are preferably given a stronglyalkaline formulation using, for example, sodium hydroxide, sodiummetasilicate, 2-aminoethanol. In addition they generally contain anionicand/or nonionic surfactants, water-soluble solvents, and, in some cases,thickeners such as polycarboxylates and carboxymethylcellulose;

Metal polishes. These are cleaners for particular types of metal such asstainless steel or silver. Stainless steel cleaners preferably contain,besides acids (preferably up to 3% by weight, e.g., citric acid, lacticacid), surfactants (in particular, up to 5% by weight, preferablynonionic and/or anionic surfactants), and water, solvents as well(preferably up to 15% by weight) to remove fatty soiling, and alsofurther compounds such as thickeners and preservatives. Very finepolishing structures are included, furthermore, in products forpreferably bright stainless steel surfaces. Silver polishes, in turn,may be provided in an acidic formulation. In particular, for removingblack deposits of silver sulfide they contain, preferably, complexingagents (e.g., thiourea, sodium thiosulfate). Typical supply forms arepolishing cloths, dipping baths, pastes, and liquids. Darkdiscolorations (oxide layers) are removed using copper cleaners andnonferrous-metal cleaners (e.g., for brass and bronze). They generallyhave a weakly alkaline formulation (preferably with ammonia) and ingeneral contain polishing agents and also, preferably, ammonium soapsand/or complexing agents;

Glass cleaners and window cleaners. These products serve preferably toremove dirt, especially greasy dirt, from glass surfaces. Preferablythey contain compounds such as anionic and/or nonionic surfactants (inparticular, up to 5% by weight), ammonia and/or ethanolamine (inparticular, up to 1% by weight), ethanol and/or 2-propanol, glycolethers (in particular, 10-30% by weight), water, preservatives, dyes,anti-misting agents and the like; and

Special-purpose cleaning products, examples being those forglass-ceramic hobs, and also carpet cleaners and stain removers.

Autocare Products Include:—

Paint preservers, paint polishes, paint cleaners, wash preservers,shampoos for auto washing, auto-wash and wax products, polishes for trimmetals, protective films for trim metals, plastics cleaners, tarremovers, screen cleaners, engine cleaners, and the like.

Cosmetic Products Include:—

(a) cosmetic skincare products, especially bath products, skin washingand cleansing products, skincare products, eye makeup, lip careproducts, nail care products, intimate care products, foot careproducts;

(b) cosmetic products with specific effects, especially sunscreens,tanning products, de-pigmenting products, deodorants, antiperspirants,hair removers, shaving products, perfumes;

(c) cosmetic dental-care products, especially dental and oral careproducts, tooth care products, cleaners for dental prostheses, adhesivesfor dental prostheses; and

(d) cosmetic hair care products, especially hair shampoos, hair careproducts, hair setting products, hair-shaping products, and haircoloring products.

Textile Treatment Products Include:—

Detergents or fabric conditioners, for example, in either liquid orsolid form.

Air Fresheners and Room Fragrances Include:—

Products that contain preferably volatile and usually pleasant-smellingcompounds which advantageously can even in very small amounts maskunpleasant odours. Air fresheners for living areas contain, inparticular, natural and synthetic essential oils such as pine needleoils, citrus oil, eucalyptus oil, lavender oil, and the like, in amountsfor example of up to 50% by weight. As aerosols they tend to containsmaller amounts of such essential oils, by way of example less than 5%or less than 2% by weight, but additionally include compounds such asacetaldehyde (in particular, <0.5% by weight), isopropyl alcohol (inparticular, <5% by weight), mineral oil (in particular, <5% by weight),and propellants. Other presentation forms include sticks and blocks.They are produced typically using a gel concentrate comprising essentialoils. It is also possible to add formaldehyde (for preservation) andchlorophyll (preferably <5% by weight), and also further ingredients.Air fresheners are not, however, restricted to living spaces, but mayalso be intended for autos, cupboards, dishwashers, refrigerators orshoes, and even their use in vacuum cleaners is a possibility. In thehousehold (e.g., in cupboards), for example, in addition to the odourimprovers, disinfectants as well are employed, containing preferablycompounds such as calcium phosphate, talc, stearin, and essential oils,these products taking the form, for example, of sachets.

Consumer product compositions referred to hereinabove, particularlythose for use in washing or cleaning applications may contain one ormore of the following substances:

Builder substances, surfactants, enzymes, bleaching agents, such aspreferably organic and/or inorganic peroxygen compounds, peroxygenactivators, water-miscible organic solvents, sequestering agents,electrolytes, pH regulators, thickeners, and further adjuvants such assoil release active substances, optical brighteners, graying inhibitors,color transfer inhibitors, foam regulators, and dyes.

Surfactant include anionic surfactants, nonionic surfactants, andmixtures thereof, but also cationic surfactants, are appropriate.Suitable nonionic surfactants are, in particular, ethoxylation and/orpropoxylation products of alkyl glycosides and/or of linear or branchedalcohols each having 12 to 18 carbon atoms in the alkyl portion and 3 to20, by preference 4 to 10, alkyl ether groups. Also usable arecorresponding ethoxylation and/or propoxylation products ofN-alkylamines, vicinal diols, fatty acid esters and fatty acid amidesthat correspond, in terms of the alkyl portion, to the aforesaidlong-chain alcohol derivatives, and of alkylphenols having 5 to 12carbon atoms in the alkyl residue.

Suitable anionic surfactants include soaps, and those that containsulfate or sulfonate groups having preferably alkali ions as cations.Soaps include alkali salts of the saturated or unsaturated fatty acidshaving 12 to 18 carbon atoms. Such fatty acids can also be used inincompletely neutralized form. Included among the usable surfactants ofthe sulfate type are the salts of the sulfuric acid semi-esters of fattyalcohols having 12 to 18 carbon atoms, and the sulfated products of theaforesaid nonionic surfactants having a low degree of ethoxylation.Included among the usable surfactants of the sulfonate type are linearalkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl portion,alkanesulfonates having 12 to 18 carbon atoms, and olefinsulfonateshaving 12 to 18 carbon atoms that are produced upon reaction ofcorresponding monoolefins with sulfur trioxide, as well asalpha-sulfofatty acid esters that are produced upon sulfonation of fattyacid methyl or ethyl esters.

Cationic surfactants include esterquats and/or the quaternary ammoniumcompounds (QACs). QACs may be produced by the reaction of tertiaryamines with alkylating agents such as methyl chloride, benzyl chloride,dimethyl sulfate, dodecyl bromide, but also ethylene oxide. Thealkylation of tertiary amines having a long alkyl residue and two methylgroups occurs particularly easily, and the quaternization of tertiaryamines having two long residues and one methyl group can also be carriedout using methyl chloride under mild conditions. Amines that possessthree long alkyl residues or hydroxy-substituted alkyl residues have lowreactivity, and are quaternized, for example, using dimethyl sulfate.Suitable QACs are, for example, benzalkonium chloride(N-alkyl-N,N-dimethylbenzylammonium chloride), benzalkon B(m,p-dichlorobenzyldimethyl-C12-alkylammonium chloride), benzoxoniumchloride (benzyldodecyl-bis(2-hydroxyethyl)ammonium chloride),cetrimonium bromide (N-hexadecyl-N,N-trimethylammonium bromide),benzetonium chloride(N,N-dimethyl-N-[2-[2-[p-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]benzylammoniumchloride), dialkyldimethylammonium chlorides such asdi-n-decyldimethylammonium chloride, didecyldimethylammonium bromide,dioctyldimethylammonium chloride, 1-cetylpyridinium chloride, andthiazoline iodide, as well as mixtures thereof. Preferred QACs are thebenzalkonium chlorides having C₈ to C₂₂ alkyl residues, in particularC₁₂ to C₁₄ alkylbenzyldimethylammonium chloride.

Esterquats include the commercially availablemethylhydroxyalkyldialkoyloxyalkylammonium methosulfates marketed by theStepan company under the trademark Stepantex™, or the products of CognisDeutschland GmbH known under the trade name Dehyquat™, or the Rewoquat™products of Goldschmidt-Witco.

Surfactants may be employed in amounts of 5 wt % to 50 wt % in aconsumer product of the present invention.

Builders include the water-soluble and/or water-insoluble, organicand/or inorganic builders. In particular, they include the water-solubleorganic builder substances are polycarboxylic acids, more particularlycitric acid and sugar acids, monomeric and polymeric aminopolycarboxylicacids, in particular methylglycinediacetic acid, nitrilotriacetic acid,and ethylenediaminetetraacetic acid, as well as polyaspartic acid,polyphosphonic acids, in particular aminotris(methylenephosphonic acid),ethylenediaminetetrakis (methylenephosphonic acid), and1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds suchas dextrin, as well as polymeric (poly)carboxylic acids, polymericacrylic acids, methacrylic acids, maleic acids, and mixed polymersthereof, which can also contain small proportions of polymerizablesubstances having no carboxylic-acid functionality. The relativemolecular weight of homopolymers of unsaturated carboxylic acids isgenerally between 5000 and 200,000, that of the copolymers between 2000and 200,000, based in each case on free acid. Suitable compounds of thisclass are copolymers of acrylic acid or methacrylic acid with vinylethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene,and styrene, in which the proportion of acid is equal to at least 50 wt%. It is also possible to use, as water-soluble organic buildersubstances, terpolymers that contain two unsaturated acids and/or saltsthereof as monomers and, as a third monomer, vinyl alcohol and/or avinyl alcohol derivative or a carbohydrate. The first acid monomer orsalt thereof may be derived from an ethylenically mono-unsaturated C₃ toC₈ carboxylic acid. The second acid monomer or salt thereof can be aderivative of a C₄ to C₈ dicarboxylic acid, for example maleic acid. Thethird monomeric unit is constituted by vinyl alcohol and/or anesterified vinyl alcohol. Polymers may contain 60 wt % to 95 wt %, inparticular 70 wt % to 90 wt %, (meth)acrylic acid or (meth)acrylate, aswell as 5 wt % to 40 wt % vinyl alcohol and/or vinyl acetate. Particularpolymers are those in which the weight ratio of (meth)acrylic acidrespectively (meth)acrylate to maleic acid or maleate is between 1:1 and4:1. Both the quantities and the weight ratios are based on the acids.The second acid monomer or salt thereof can also be a derivative of anallylsulfonic acid that is substituted in the 2-position with an alkylradical, e.g. a C₁ to C₄ alkyl radical, or with an aromatic radical thatmay be derived from benzene or benzene derivatives. Terpolymers maycontain 40 wt % to 60 wt %, in particular 45 to 55 wt %, (meth)acrylicacid or (meth)acrylate, particularly preferably acrylic acid oracrylate, 10 wt % to 30 wt %, by preference 15 wt % to 25 wt %methallylsulfonic acid or methallylsulfonate, and as a third monomer 15wt % to 40 wt %, by preference 20 wt % to 40 wt % of a carbohydrate.This carbohydrate can be, for example, a mono-, di-, oligo-, orpoly-saccharide, e.g. sucrose. The terpolymers generally have a relativemolecular weight between 1000 and 200,000. Further copolymers includethose that comprise, as monomers, acrolein and acrylic acid/acrylic acidsalts, or vinyl acetate. Especially for the manufacture of liquiddetergents, the organic builder substances can be used in the form ofaqueous solutions, for example a 30- to 50-weight-percent aqueoussolutions. All the aforesaid acids may be used in the form of theirwater-soluble salts, in particular their alkali salts.

Organic builder substances can be employed in quantities of up to 40 wt%.

Water-soluble inorganic builder materials include alkali silicates andpolyphosphates, e.g. sodium triphosphate. Crystalline or amorphousalkali aluminosilicates, e.g. crystalline sodium aluminosilicates, mayalso be employed as water-insoluble, water-dispersible inorganic buildermaterials, in quantities of up to 50 wt %, for example. Aluminosilicatestypically comprise particles having a particle size less than 30 μm.

Crystalline alkali silicates may also be employed, either alone or usedwith amorphous silicates. The alkali silicates usable in consumerproducts of the present invention as detergency builders may have amolar ratio of alkali oxide to SiO₂ below 0.95, in particular from 1:1.1to 1:12, and can be present in amorphous or crystalline fashion. Thealkali silicates may be sodium silicates, in particular the amorphoussodium silicates, having a Na₂O:SiO₂ molar ratio from 1:2 to 1:2.8.

Builder substances may be contained in consumer product compositionsaccording to the present invention at levels up to 60 wt %.

Peroxygen compounds include organic peracids or peracid salts of organicacids such as phthalimidopercapronic acid, perbenzoic acid, or salts ofdiperdodecanedioic acid, hydrogen peroxide, and inorganic salts thatrelease hydrogen peroxide under application conditions, such asperborate, percarbonate, and/or persilicate. If solid peroxygencompounds are to be used, they can be utilized in the form of powders orgranulates, which in principle can also be encased in known fashion.

Peroxygen compounds may be employed in amounts up to 50 wt %. Theaddition of small quantities of known bleaching-agent stabilizers, forexample phosphonates, borates respectively metaborates, andmetasilicates, as well as magnesium salts such as magnesium sulfate, maybe useful.

Compounds that, under perhydrolysis conditions, yield aliphaticperoxocarboxylic acids having preferably 1 to 10 carbon atoms, inparticular 2 to 4 carbon atoms, and/or (optionally substituted)perbenzoic acid, can be used as bleach activators. Substances that carryO- and/or N-acyl groups having the aforesaid number of carbon atoms,and/or optionally substituted benzoyl groups, are suitable. Multipleacylated alkylenediamines, in particular tetraacetylethylendiamine(TAED), acylated triazine derivatives, in particular1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylatedglycolurils, in particular tetraacetyl glycoluril (TAGU), N-acylimides,in particular N-nonanoyl succinimide (NOSI), acylated phenolsulfonates,in particular n-nonanoyl or isononanoyl oxybenzenesulfonate (n- oriso-NOBS), carboxylic acid anhydrides, in particular phthalic acidanhydride, acylated polyvalent alcohols, in particular triacetin,ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, and enolesters, as well as acetylated sorbitol and mannitol respectivelymixtures thereof (SORMAN), acylated sugar derivatives, in particularpentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose andoctaacetyllactose, as well as acetylated, optionally N-alkylatedglutamine and gluconolactone, and/or N-acylated lactams, for exampleN-benzoylcaprolactam, may be employed. Hydrophilically substituted acylacetates and acyl lactams may likewise be employed. Combinations ofconventional bleach activators can also be used. Such bleach activatorscan be contained in the usual quantity range, by preference inquantities from 1 wt % to 10 wt %, in particular 2 wt % to 8 wt %, basedon the entire agent.

In addition to or instead of the aforementioned conventional bleachactivators, sulfonimines and/or bleach-intensifying transition metalsalts or transition metal complexes can also be contained as bleachcatalysts. Included among the appropriate transition metal compoundsare, in particular, salen complexes of manganese, iron, cobalt,ruthenium, or molybdenum and nitrogen-analog compounds thereof, carbonylcomplexes of manganese, iron, cobalt, ruthenium, or molybdenum,complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium,vanadium, and copper having nitrogen-containing tripod ligands, aminecomplexes of cobalt, iron, copper, and ruthenium. Combinations of bleachactivators and transition metal bleach catalysts can likewise be used.Bleach-intensifying transition metal complexes, in particular having thecentral atoms Mn, Fe, Co, Cu, Mo, V, Ti, and/or Ru, can be used inconventional quantities, such as up to 1 wt % based on the weight of theconsumer product composition.

Suitable enzymes that may be employed in compositions are those from theclass of the proteases, cutinases, amylases, pullulanases,hemicellulases, cellulases, lipases, oxidases, and peroxidases, as wellas mixtures thereof. Enzymatically active substances recovered fromfungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis,Streptomyces griseus, Humicola lanuginosa, Humicola insolens,Pseudomonas pseudoalcaligenes, or Pseudomonas cepacia, are alsosuitable. The enzymes that are used as applicable can be adsorbed ontocarrier substances and/or embedded into encasing substances in order toprotect them from premature inactivation. They may be contained inwashing products according to the present invention in amounts typicallybelow 5 wt %.

Optical brighteners include derivatives of diaminostilbenedisulfonicacid or alkali metal salts thereof. Suitable, for example, are salts of4,4′-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2′-disulfonicacid, or compounds of similar structure that carry, instead of themorpholino group, a diethanolamino group, a methylamino group, ananilino group, or a 2-methoxyethylamino group. Brighteners of thesubstituted diphenylstyryl type can also be present, e.g. the alkalisalts of 4,4′-bis(2-sulfostyryl)diphenyl, of4,4′-bis(4-chloro-3-sulfostyryl)diphenyl, or of4-(4-chlorostyryl)-4′-(2-sulfostyryl)diphenyl. Mixtures of the aforesaidoptical brighteners can also be used.

Foam inhibitors include organopolysiloxanes and mixtures thereof withmicrofine, optionally silanated silicic acid, as well as paraffin waxesand mixtures thereof with silanated silicic acid or bis-fatty acidalkylenediamides. Mixtures of different foam inhibitors, for examplethose made of silicones, paraffins, or waxes, can also be employed. Thefoam inhibitors, in particular silicone- and/or paraffin-containing foaminhibitors are by preference bound to a granular carrier substance thatis soluble or dispersible in water. Mixtures of paraffins andbistearylethylenediamide, in particular may be employed.

Soil release active substances are those compounds that positivelyinfluence the ability of oils and fats to be washed out of textiles.This effect becomes particularly apparent when the soiled textile is onethat has already been previously washed several times with a washingagent according to the present invention that contains this oil- andfat-releasing component. The preferred oil- and fat-releasing componentsinclude, for example, nonionic cellulose ethers such as methyl celluloseand methylhydroxypropyl cellulose having a 15 to 30 wt % proportion ofmethoxy groups and a 1 to 15 wt % proportion of hydroxypropoxyl groups,based in each case on the nonionic cellulose ethers, as well aspolymers, known from the existing art, of phthalic acid and/orterephthalic acid resp. of their derivatives with monomeric and/orpolymeric diols, in particular polymers of ethylene terephthalatesand/or polyethylene glycol terephthalates or anionically and/ornonionically modified derivatives thereof.

Colour transfer inhibitors include polymers of vinylpyrrolidone,vinylimidazole, vinylpyridine-N-oxide, or copolymers thereof. Alsousable are both polyvinylpyrrolidones having molecular weights from15,000 to 50,000 and polyvinylpyrrolidones having molecular weightsabove 1,000,000, in particular from 1,500,000 to 4,000,000,N-vinylimidazole/N-vinylpyrrolidone copolymers, polyvinyloxazolidones,copolymers based on vinyl monomers and carboxylic acid amides,pyrrolidone-group-containing polyesters and polyamides, graftedpolyamidoamines and polyethylenimines, polymers having amide groups madeup of secondary amines, polyamine-N-oxide polymers, polyvinyl alcohols,and copolymers based on acrylamidoalkenyl sulfonic acids. It is alsopossible, however, to use enzymatic systems encompassing a peroxidaseand hydrogen peroxide or a substance that yields hydrogen peroxide inwater.

Graying inhibitors are those materials that keep dirt that has beendetached from the textile fibers suspended in a washing medium.Water-soluble colloids, usually organic in nature, are suitable forthis, for example starch, size, gelatin, salts of ethercarboxylic orethersulfonic acids of starch or of cellulose, or salts of acid sulfuricacid esters of cellulose or of starch. Water-soluble polyamidescontaining acid groups are also suitable for this purpose. Starchderivatives other than those recited above can also be used, for examplealdehyde starches. Cellulose ethers such as carboxymethyl cellulose(sodium salt), methyl cellulose, hydroxyalkyl cellulose, and mixedethers such as methylhydroxyethyl cellulose, methylhydroxypropylcellulose, methylcarboxymethyl cellulose, and mixtures thereof may beused, for example in quantities from 0.1 to 5 wt % based on the weightof the consumer product.

Organic solvents include alcohols having 1 to 4 carbon atoms, inparticular methanol, ethanol, isopropanol, and tert-butanol, diolshaving 2 to 4 carbon atoms, in particular ethylene glycol and propyleneglycol, as well as mixtures thereof, and the ethers derivable from theaforesaid compound classes. Water-miscible solvents of this kind arepresent in washing products according to the present invention inamounts typically not exceeding 30 wt %.

pH regulators include citric acid, acetic acid, tartaric acid, malicacid, lactic acid, glycolic acid, succinic acid, glutaric acid, and/oradipic acid, but also mineral acids, in particular sulfuric acid, orbases, in particular ammonium hydroxides or alkali hydroxides. pHregulators of this kind are contained in the agents according to thepresent invention in quantities preferably not above 20 wt %, inparticular from 1.2 wt % to 17 wt %.

The compounds are may be particularly used to perfume household productscontaining enzymes, such as those defined above, and in particulartextile treatment products, such as detergents, containing enzymes.

There now follows a series of examples that serve to further illustratethe invention.

EXAMPLE 1

Synthesis of 3-(4-isobutyl-2-methylphenyl)propanal

A) 1-Isobutyl-4-(3-(methoxymethoxy)propyl)benzene:

To a solution of 3-(4-isobutylphenyl)propan-1-ol (641.0 g, 3.33 mol) in1.5 L of dimethoxymethane was added lithium bromide (14.5 g) andp-toluene sulfonic acid (10.0 g). The mixture was stirred for 20 h atroom temperature and then poured with stirring into aqueous sodiumhydroxide (200 ml, 2M). The organic phase was washed neutral with adiluted solution of NaCl, dried (MgSO₄) and evaporated in vacuo to yield1-isobutyl-4-(3-(methoxymethoxy)propyl)benzene (721.0 g, 91.5%) as acolourless oil. ¹H-NMR (400 MHz, CDCl3): δ=7.17-7.08 (m, 4H), 4.68 (s,2H), 3.59 (t, J=6.4 Hz, 2H), 3.42 (s, 3H), 2.74 (t, J=7.8 Hz, 2H), 2.49(d, J=7.1 Hz, 2H), 2.0-1.84 (m, 3H), 0.95 (d, J=6.6 Hz, 6H) ppm. ¹³C-NMR(400 MHz, CDCl3): δ=139.5 (s), 139.4 (s), 129.5 (d, 2C), 128.5 (d, 2C),96.9 (t), 67.6 (t), 55.6 (q), 45.5 (t), 32.5 (t), 31.9 (t), 30.7 (d),22.8 (q, 2C) ppm. GC/MS (EI): 236 (M⁺), 204 (29), 161 (65), 147 (59),131 (100), 117 (49), 105 (37), 104 (26), 91 (46), 57 (29), 45 (64).

B) 8-Isobutyl-1,3,4,5-tetrahydrobenzo[c]oxepine:

To a cooled solution (0° C.) of AlCl₃ (10.33 g) in dichlormethane (80ml) was added dropwise a solution of1-isobutyl-4-(3-(methoxymethoxy)propyl)benzene (13.9 g, 55.36 mmol) indichloromethane (40 ml). After the addition was complete, the mixturewas stirred for 1.5 h at 5° C. and poured into an aqueous sodiumhydroxide solution (80 ml, 2M). The mixture was extracted with MTBE andthe organic phases were washed with after and brine, dried (MgSO₄) andevaporated in vacuo to afford a clear yellowish oil (11.91 g) which wasfirst distilled in kugelrohr (125° C., 0.12 mbar) and then purified bychromatography to yield 8-isobutyl-1,3,4,5-tetrahydrobenzo[c]oxepine(6.95, 61%) as a colourless oil. Odor: ¹H NMR (400 MHz, CDCl₃): δ=7.11(d, J=7.33 Hz, 1H), 7.01-6.97 (m, 2H), 4.66 (s, 2H), 4.09-4.06 (m, 2H),3.02-2.98 (m, 2H), 2.46 (d, J=7.33 Hz, 2H), 1.93-1.82 (m, 1H), 0.94 (d,J=6.8 Hz, 6H) ppm. ¹³C-NMR (400 MHz, CDCl₃): δ=140.3 (s), 140.05 (s),139.9 (s), 129.8 (d), 129.3 (d), 128.8 (d), 76.1 (t), 75.6 (t), 45.3(t), 35.5 (t), 30.9 (t), 30.6 (d), 22.8 (q, 2C) ppm. GC/MS (EI): 204(M⁺, 33), 161 (100), 147 (44), 143 (58), 131 (31), 129 (28), 119 (61),115 (34), 105 (43), 91 (34).

C) 3-(4-Isobutyl-2-methylphenyl)propan-1-ol

A catalytic amount of borontriflouride etherate (0.3 g) was added to asuspension of Pd/C (10%, 0.5 g) and8-isobutyl-1,3,4,5-tetrahydrobenzo[c]oxepine (50.0 g, 244.7 mmol). Themixture was hydrogenated in an autoclave for 2 h at 9 bar and 50° C. Thesuspension was filtered and thin film distilled (160° C., 0.11 mbar) toyield 3-(4-isobutyl-2-methylphenyl)propan-1-ol (45.4 g, 89.9%) as aviscous colourless oil. Odour: ¹H-NMR (400 MHz, CDCl₃): δ=7.10 (d, J=7.6Hz, 1H), 6.99-6.94 (m, 2H), 3.75 (t, J=6.6 Hz, 2H), 2.74-2.68 (m, 2H),2.47 (d, J=7.3 Hz, 2H), 2.34 (s, 3H), 2.19 (s, 1H, —OH), 1.95-1.84 (m,1H), 0.96 (d, J=6.6 Hz, 6H) ppm. ¹³C-NMR (400 MHz, CDCl3): δ=139.7 (s),137.6 (s), 135.9 (s), 131.5 (d), 128.9 (d), 127.1 (d), 63.0 (t), 45.4(t), 33.5 (t), 30.6 (d), 29.5 (t), 22.9 (q), 19.7 (q) ppm. GC/MS (EI):206 (M⁺, 25), 163 (100), 161 (27), 145 (84), 119 (53), 117 (33), 115(32), 105 (41), 91 (40), 41 (23).

D) 3-(4-Isobutyl-2-methylphenyl)propanal

Pyridinium chlorochromate (PCC, 37.6 g, 174.49 mmol) was addedportionwise to a solution of 3-(4-isobutyl-2-methylphenyl)propan-1-ol(30.0 g, 145.41 mmol) in dichloromethane (300 ml); the temperature roseto 35° C. The mixture was stirred for 1 h and another portion of PCC (10g, 46.4 mmol) was added and stirring was continued for another 15 min.The reaction mixture was filtered over Florisil and silica gel. Thefiltrate was evaporated in vacuo (23.2 g) and distilled in kugelrohr(143° C., 0.08 mbar) to yield 3-(4-isobutyl-2-methylphenyl)propanal(19.01 g, 64%) as a colorless oil. Odor: floral, aldehydic, green,Lilial, watery. ¹H-NMR (400 MHz, CDCl3): δ=9.88 (t, J=1.5 Hz, 1H), 7.07(d, J=7.6 Hz, 1H), 7.0-6.95 (m, 2H), 2.98-2.93 (m, 2H), 2.79-2.74 (m,2H), 2.46 (d, J=7.1 Hz, 2H), 2.33 (s, 3H), 1.95-1.82 (m, 1H), 0.95 (d,J=6.6 Hz, 6H) ppm. ¹³C-NMR (400 MHz, CDCl3): δ=202.2 (d), 140.2 (s), 136(s), 135.9 (s), 131.6 (d), 128.6 (d), 127.3 (d), 45.4 (t), 44.6 (t),30.6 (d), 25.5 (t), 22.9 (q), 19.7 (q) ppm. GC/MS (EI): 204 (M⁺, 23),161 (100), 147 (26), 143 (49), 119 (84), 118 (34), 117 (33), 115 (33),105 (59), 91 (36).

The following compounds were prepared according to the sequencedescribed in Example 1

EXAMPLE 2

3-(4-Isobutyl-2,6-dimethylphenyl)propanal

Odor: floral, aldehydic, fruity, slightly rosy

¹H NMR (400 MHz, CDCl₃): δ=9.91-9.89 (t, J=1.5 Hz, 1H), 6.84 (s, 2H),2.99-2.93 (m, 2H), 2.67-2.61 (m, 2H), 2.42-2.39 (d, J=7.1 Hz, 2H), 2.32(s, 6H), 1.94-1.80 (m, 1H), 0.96-0.92 (d, J=6.57, 6H) ppm. ¹³C NMR (400MHz, CDCl₃): β=202.1 (d), 139.9 (s), 136.0 (s, 2C), 134.5 (s), 129.6 (d,2C), 45.4 (t), 43.6 (t), 30.5 (d), 22.9 (q, 2C), 22.1 (t), 20.1 (q, 2C)ppm. GC/MS (EI): 218 (M⁺), 175 (81), 162 (31), 157 (55), 133 (71), 132(29), 119 (100), 117 (29), 115 (37), 105 (31), 91 (47).

EXAMPLE 3

3-(4-Isobutyl-2-methylphenyl)-2-methylpropanal

Odor: fatty, watery, floral, green, aldehydic

¹H NMR (400 MHz, CDCl₃): δ=9.75 (d, J=1.8 Hz, 1H), 7.03 (d, J=7.6 Hz,1H), 6.99-6.92 (m, 2H), 3.09 (dd, J=6.1 Hz, 13.9 Hz, 1H), 2.73-2.73 (m,1H), 2.61-2.54 (m, 1H), 2.44 (d, J=7.1 Hz, 2H), 2.32 (s, 3H), 1.94-1.81(m, 1H), 1.14 (d, J=6.8 Hz, 3H), 0.93 (d, J=6.6 Hz, 6H) ppm. ¹³C NMR(400 MHz, CDCl₃): δ=204.9 (d), 140.3 (s), 136.1 (s), 134.6 (s), 131.7(d), 129.8 (d), 127.1 (d), 47.3 (d), 45.4 (t), 34.0 (t), 30.6 (d), 22.8(q), 19.9 (q), 13.9 (q) ppm. GC/MS (EI): 218 (M⁺), 161 (100), 119 (62),118 (24), 117 (23), 115 (23), 106 (16), 105 (81), 91 (31), 43 (27), 41(25).

EXAMPLE 4

3-(4-Isobutyl-2-methylphenyl)butanal

Odor: floral, green, watery, fatty

¹H NMR (400 MHz, CDCl₃): δ=9.74 (t, J=1.8 Hz, 1H), 7.10 (d, J=7.8 Hz,1H), 6.01-6.95 (m, 2H), 3.64-3.55 (m, 1H), 2.77 (ddd, J=1.8 Hz, 6.7 Hz,16.7 Hz,1H), 2.67 (ddd, J=2.2 Hz, 8.1 Hz, 16.5 Hz, 1H), 2.43 (d, J=7.3Hz, 2H), 2.37 (s, 3H), 1.92-1.82 (m, 1H), 1.30 (d, J=6.8 Hz, 3H), 0.93(d, J=6.8 Hz, 6H) ppm. ¹³C NMR (400 MHz, CDCl₃): δ=202.5 (d), 141.1 (s),139.9 (s), 135.0 (s), 131.8 (d), 127.5 (d), 125.4 (d), 51.7 (t), 45.4(t), 30.6 (d), 29.5 (d), 22.9 (q), 22.6 (q), 19.8 (q) ppm. GC/MS (EI):218 (M⁺),175 (100), 161 (25), 133 (43), 131 (28), 119 (22), 117 (28),115 (25), 105 (16), 105 (61), 91 (28), 41 (21).

EXAMPLE 5

3-(4-(sec-Butyl)-2-methylphenyl)propanal

Odor: green, floral, marine, Lilial-like

¹H NMR (400 MHz, CDCl₃): δ=9.89 (t, J=1.5 Hz, 1H), 7.08 (d, J=7.3 Hz,1H), 7.02-6.98 (m, 2H), 2.98-2.93 (m, 2H), 2.80-2.74 (m, 2H), 2.56 (m,J=7.1 Hz, 1H), 2.34 (s, 3H), 1.67-1.56 (m, 2H), 1.26 (d, J=6.8 Hz, 3H),0.87 (t, J=7.5 Hz, 3H) ppm. ¹³C NMR (400 MHz, CDCl₃): δ=202.2 (d), 146.3(s), 136.1 (s), 136.0 (s), 129.6 (d), 128.7 (d), 125.2 (d), 44.5 (t),41.6 (d), 31.6 (t), 25.5 (t), 22.2 (q), 19.8 (q), 12.7 (q) ppm. GC/MS(EI): 204 (M⁺), 175 (100), 147 (14), 133 (16), 131 (54), 119 (32), 117(26), 115 (27), 105 (27), 91 (35), 77 (14).

EXAMPLE 6

3-(2-Methyl-4-(tert-pentyl)phenyl)propanal

Odor: floral, green, weak

¹H NMR (400 MHz, CDCl₃): δ=9.89 (t, J=1.5 Hz, 1H), 7.16-7.07 (m, 3H),2.99-2.93 (m, 2H), 2.80-2.74 (m, 2H), 2.35 (s, 3H), 1.67 (q, 3=7.6 Hz,2H), 1.30 (s, 6H), 0.74 (t, J=7.6 Hz, 3H) ppm. ¹³C NMR (400 MHz, CDCl₃):δ=202.2 (d), 148.1 (s), 135.6 (s), 128.4 (d, 2C), 124.2 (d), 44.5 (t),37.9 (s), 37.2 (t), 28.8 (q, 2C), 25.4 (t), 20.1 (q), 9.6 (q) ppm. GC/MS(EI): 218 (M⁺), 190 (15), 189 (100), 145 (42), 131 (15), 129 (10), 128(11), 115 (16), 105 (16), 91 (18), 41 (12).

EXAMPLE 7

3-(4-Isopentyl-2-methylphenyl)propanal

Odor: aldehydic, floral, green, watery

¹H NMR (400 MHz, CDCl₃): δ=9.87 (t, J=1.5 Hz, 1H), 7.06 (d, J=7.8 Hz,1H), 7.02-6.97 (m, 2H), 2.96-2.91 (m, 2H), 2.78-2.72 (m, 2H), 2.60-2.54(m, 2H), 2.32 (s, 3H), 1.67-1.55 (m, 1H), 1.54-1.46 (m, 2H), 0.96 (d,J=6.6, 6H) ppm. ¹³C NMR (400 MHz, CDCl₃): δ=202.2 (d), 141.7 (s), 136.1(s), 135.9 (s), 130.9 (d), 128.8 (d), 126.5 (d), 44.6 (t), 41.3 (t),33.7 (t), 28.1 (d), 25.5 (t), 22.9 (q, 2C), 19.7 (q) ppm. GC/MS (EI):218 (M⁺), 119 (37), 118 (100), 117 (23), 115 (22), 106 (31), 105 (36),91 (28), 43 (22), 41 (29), 29 (20).

EXAMPLE 8

3-(5-Isopropyl-2-methylphenyl)butanal

Odor: floral fruity, slightly rosy, slightly green

¹H NMR (400 MHz, CDCl₃): δ=9.77 (dd, J=1.8 Hz, 2.2 Hz, 1H), 7.13 (d,J=7.8 Hz, 1H), 7.09-7.02 (m, 2H), 3.69-3.59 (m, 1H), 2.92 (sp, J=6.8 Hz,1H), 2.81 (ddd, J=1.7 Hz, 6.2 Hz, 16.6 Hz, 1H), 2.72 (ddd, J=2.2 Hz, 8.3Hz, 16.7 Hz, 1H), 2.38 (s, 3H), 1.34 (d, J=6.8 Hz, 3H), 1.29 (d, J=6.8Hz, 6H) ppm. ¹³C NMR (400 MHz, CDCl₃): δ=202.3 (d), 147.4 (s), 143.8(s), 132.8 (s), 130.9 (d), 124.5 (d), 123.9 (d), 51.6 (t), 34.3 (d),29.8 (d), 24.5 (q), 21.9 (q), 19.4 (q) ppm. GC/MS (EI): 204 (M⁺), 161(54), 147 (27), 145 (38), 119 (100), 117 (25), 115 (32), 105 (43), 91(42), 43 (31), 41 (31).

EXAMPLE 9

5-Isobutyl-2,3-dihydro-1H-indene-2-carbaldehyde

Odor: aldehydic, marine, watery, floral

¹H NMR (400 MHz, CDCl₃): β=9.80 (d, J=1.8 Hz, 1H), 7.15 (d, J=7.6 Hz,1H), 7.04 (s, 1H), 6.98 (d, J=7.3 Hz, 1H), 3.34-3.25 (m, 3H), 3.24-2.96(m, 2H), 2.47 (d, J=7.1 Hz, 2H), 1.93-1.73 (m, J=6.82, 1H), 0.93 (d,J=6.6H, 6H) ppm. ¹³C NMR (400 MHz, CDCl₃): δ=203.4 (d), 141.5 (s), 140.9(s), 138.7 (s), 128.2 (d), 125.7 (d), 124.5 (d), 51.3 (d), 45.7 (t),33.3 (t), 33.0 (t), 30.7 (d), 22.8 (q, 2C) ppm. GC/MS (EI): 202 (M⁺ 35),159 (100), 145 (32), 141, (47), 131 (17), 129 (91), 128 (70), 127 (23),115 (43), 41 (21).

EXAMPLE 10

Synthesis of 3-(2-Methyl-4-(4-methylpentyl)phenyl)propanal

E) (E)-3-(2-methyl-4-(4-methylpent-3-en-1-yl)phenyl)acrylaldehyde:

To a solution of 2-methyl-4-(4-methylpent-3-en-1-yl)benzaldehyde (3.0 g,14.8 mmol) and trimethylorthoformate (2.36 g, 22.3 mmol) in methanol (2ml) at 0° C., was added acetyl chloride (0.05 g, 0.64 mmol). The mixturewas stirred at room temperature for 30 min and then aqueous sodiumbicarbonate (2.0 ml) was added. The organic layer was separated,concentrated and dissolved again in diethyl ether (2.0 ml).Borontrifluoride etherate (0.11 g, 0.74 mmol) was added dropwisefollowed by ethoxyethene (1.40 g, 19.3 mmol). The reaction mixture wasstirred at room temperature for 30 min, aqueous sodium bicarbonate (2.0ml) was added, and the organic layer was separated. The organic layerwas dried (MgSO₄). The solvent was evaporated in vacuo and aqueous HClsolution (7.4%, 5.0 ml) was added to the residue. The mixture was heatedto reflux for 5 h and then cool to room temperature. The reaction wasdiluted by water (15 ml) and then extracted by MTBE (2×15 ml). Theorganic layers were dried over MgSO₄ and evaporated in vacuo. The crudeproduct was purified by column chromatography to yield(E)-3-(2-methyl-4-(4-methylpent-3-en-1-yl)phenyl)acrylaldehyde (1.1 g,32.5%) as a colourless oil. ¹H-NMR (300 MHz, CDCl₃): δ=9.70 (d, J=7.7Hz, 1H, CHO), 7.75 (d, J=15.7 Hz, 1H, Ar—CH═CH—), 7.57-7.50 (m, 1H,Ar—H), 7.12-7.03 (m, 2H, Ar—H), 6.65 (dd, J=7.7 Hz, 15.7 Hz, 1H,═CH—CHO), 5.15 (t, J=6.4 Hz, 1H), 2.62 (t, J=7.8 Hz, 2H), 2.46 (s, 3H,Ar—CH₃), 2.33-2.25 (m, 2H), 1.69 (s, 3H, CH₃), 1.57 (s, 3H, CH₃) ppm.¹³C-NMR (300 MHz, CDCl3): δ=193.9 (d), 150.4 (d), 146.1 (s), 137.9 (s),132.5 (s), 131.2 (d), 130.3 (s), 128.7 (d), 126.9 (d), 126.8 (d), 123.3(d), 36.0 (t), 29.7 (t), 25.7 (q), 19.8 (q), 19.7 (q) ppm. GC/MS (EI):228 (22, M⁺), 213 (22), 200 (1), 185 (2), 171 (4), 160 (100), 145 (34),131 (28), 115 (27), 103 (4), 91 (20), 79 (8), 69 (75), 53 (6), 41 (36).

F) 3-(2-Methyl-4-(4-methylpentyl)phenyl)propanal

In a 100 mL round-bottomed flask was added(E)-3-(2-methyl-4-(4-methylpent-3-en-1-yl)phenyl)acrylaldehyde (1.0 g,2.9 mmol) in ethyl acetate (15 ml) to give a colorless solution. Thesolution was de-gassed and purged with argon. Palladium on charcoal (0.1g, Pd content of 10%) was added. The reaction was stirred under hydrogenatmosphere for 2 h until completion of the conversion (confirmed by GC).The reaction mixture was filtered through a small pad of silica gel andthe solid was rinsed with ethyl acetate. The filtrate was collected andconcentrated. The residue obtained was distilled by Kugelrohr to give0.8 g of 3-(2-Methyl-4-(4-methylpentyl)phenyl)propanal as a colorlessliquid. Odor: floral, green, watery. ¹H NMR (CDCl₃): δ=9.85-9.80 (m, 1H,CHO), 7.09-6.80 (m, 3 H, Ar—H), 2.89 (t, J=7.3 Hz, 2 H, Ar—CH₂—CH₂—CHO),2.71 (t, J=7.3 Hz, 2 H, Ar—CH₂—CH₂—CHO), 2.51 (t, J=7.8 Hz, 2 H,Ar—CH₂—CH₂—CH₂), 2.28 (s, 3 H, Ar—CH₃), 1.70-1.50 (m, 3 H,(CH₃)₂CH—CH₂—CH₂), 1.32-1.15 (m, 2 H, Ar—CH₂—CH₂—CH₂—), 0.87 (d, J=6.5Hz, 6 H, 2 CH₃). ¹³C NMR (CDCl₃): δ=201.8 (d), 141.1 (s), 135.7 (s),135.6 (s), 130.5 (d), 128.4 (d), 126.1 (d), 44.2 (t), 38.8 (t), 35.8(t), 29.5 (t), 27.9 (d), 25.1 (t), 22.6 (q), 19.3 (q). MS: m/z (%)=232(89) [M⁺], 214 (80), 204 (4), 189 (100), 176 (21), 161 (68), 147 (84),129 (40), 119 (87), 105 (90), 91 (44), 77 (15), 65 (7), 55 (15), 43(27).

EXAMPLE 11

Synthesis of 3-(2-Methyl-5-(4-methylpentyl)phenyl)propanal

G) (E)-2-Bromo-1-methyl-4-(4-methylpent-1-en-1-yl)benzene:

Preparation of the Grignard Reagent:

In a 250 mL three-necked flask was added magnesium turnings (2.44 g, 100mmol), and 10 mL of anhydrous ether. Under argon atmosphere, withvigorous stirring was added 1-bromo-3-methylbutane (15.2 g in 50 mLether) dropwise. Initially, 5 mL was added in order to initiate thereaction and the reaction temperature increased from RT to 40° C. Thenthe reaction mixture was cooled to 5 degree by an ice-water bath. Withvigorously stirring, the rest of 1-bromo-3-methylbutane was addeddropwise in half an hour. After compl5etion of the addition, thereaction was refluxed for half an hour.

The Grignard Addition and Dehydration:

In a 250 mL three-necked flask was added 3-bromo-4-methylbenzaldehyde(10 g, 50 mmol) in ether (25 mL). Under argon atmosphere, the reactionmixture was cooled to 5 degree in an ice-water bath. The Grignardreagent prepared above was transferred into a 250 mL dropping funnel andwas slowly added to the reaction mixture with vigorous stirring. Theaddition took 60 min during which time the reaction temperature was keptbelow 15° C. After completion of the addition, the reaction was heatedto reflux for 10 min. The reaction mixture was cooled to 5 degree again.Then sat. NH₄Cl (aq. 75 mL) was added dropwise to quench the reaction.The organic layer was separated and the aqueous layer was extracted byether (50 mL). The combined organic layers were washed once with brine(25 mL) and then dried with MgSO₄. The Solvent was evaporated to give alight yellow liquid which was transferred to a 250 mL round-bottomedflask and dissolved in toluene (100 ml). Then 4-methylbenzenesulfonicacid hydrate (0.87 g, 5.0 mmol) was added. Under argon atmosphere, thereaction mixture was refluxed via a Dean-Stark to remove water (oil bathtemperature 135 degree). After 2 h, all water had been removed. GCanalysis indicated completion of the conversion. The reaction wasallowed to cool to room temperature. Then a slurry of NaHCO₃ salts (4.0g) in water was added with vigorous stirring. After 10 min, the reactionwas filtered and the solid was rinsed twice with toluene. The filtratewas collected and concentrated to give a yellowish liquid (39.8 g). Theyellow liquid was further purified by Kugelrohr distillation to give11.6 g of (E)-2-bromo-1-methyl-4-(4-methylpent-1-en-1-yl)benzene as acolorless liquid. ¹H NMR (CDCl₃): δ=7.43 (s, 1 H, Ar—H), 7.15-7.01 (m, 2H, Ar—H), 6.21-6.02 (m, 2 H), 2.27 (s, 3H, Ar—CH₃), 1.99 (dd, J=6.6 Hz,6.6 Hz, 2 H, —CH₂—), 1.72-1.56 (m, 1 H), 0.84 (d, J=6.6 Hz, 6 H, 2CH₃).¹³C NMR (CDCl₃): δ=137.5 (s), 136.0 (s), 130.7 (d), 130.5 (d), 129.6(d), 129.3 (d), 125.1 (s), 124.8 (d), 42.4 (t), 28.6 (d), 22.6 (q), 22.4(q). MS: m/z (%)=252 (15) [M⁺], 209 (12), 196 (15), 130 (100), 115 (22),77 (4), 63 (3), 51 (3), 41 (3).

H) (E)-(2-Methyl-5-(4-methylpent-1-en-1-yl)phenyl)boronic acid:

To a solution of (E)-2-bromo-1-methyl-4-(4-methylpent-1-en-1-yl)benzene(11.6 g, 46 mmol) in THF (50 mL) which was cooled to −78° C. in anacetone-dry ice bath was added n-BuLi (32 mL, 1.6 M in hexane, 51 mmol)dropwise. During the addition, the reaction temperature was kept below−60 degree. After completion of the addition, the reaction was stirredat −78° C. for 30 min. Then a solution of trimethyl borate (5.2 g, 51mmol) in THF (12 ml) was added dropwise to the reaction mixture at −78°C. After completion of the addition, the reaction temperature was raisedto 0° C. in 1 h and then quenched by 2N aqueous HCl (45 mL, 90 mmol).The organic layer was separated and the aqueous layer was extracted with2×50 mL MTBE. The combined organic layers were washed once with brineand then dried over MgSO₄. The solvent was evaporated and the residuewas dried under vacuum to give 13.5 g yellow solid. The solid wasre-crystallized in iso-hexane and MTBE to give 8.1 g of(E)-(2-methyl-5-(4-methylpent-1-en-1-yl)phenyl)boronic acid as a whitesolid. ¹H NMR (CDCl₃): δ=8.23 (s, 1H, Ar—H), 7.43-7.05 (m, 2H, Ar—H),6.42-6.15 (m, 2H), 2.80 (s, 3H, Ar—CH₃), 2.09 (dd, J=6.4 Hz, 6.4 Hz, 2H), 1.79-1.66 (m, 1 H, (CH₃)₂CH—), 0.96 (d, J=6.4 Hz, 6 H, 2CH₃). ¹³CNMR (CDCl₃): δ=144.8 (s), 134.9 (d), 134.7(s), 130.9 (d), 130.5 (d),129.2 (d), 125.8 (d), 42.5 (t), 28.7 (d), 22.4 (q).

I) (E)-3-(2-Methyl-5-(4-methylpent-1-en-1-yl)phenyl)propanal

To a 250 mL round-bottomed flask was added [RhCl(cod)]₂ (0.0026 g,0.0058 mmol), cycloocta-1,5-diene (0.062 g, 0.58 mmol), and potassiumphosphate (2.45 g, 11.6 mmol) in dioxane (20 ml) and water (3.0 mL) togive a yellowish solution.(E)-(2-Methyl-5-(4-methylpent-1-en-1-yl)phenyl)boronic acid (2.52 g,11.6 mmol) and acroleine (0.97 g, 17.3 mmol) were added. The reactionmixture was heated to 85° C. under argon atmosphere for 4 h. The mixturewas cooled to room temperature and was diluted with water (15 mL). Thereaction mixture was extracted with 2×50 mL MTBE. The combined organiclayers were washed once with brine and then dried over MgSO₄. Thesolvent was evaporated and the crude product was purified by columnchromatography (iso-hexane/MTBE=20:1) and Kugelrohr distillation to give0.8 g of (E)-3-(2-methyl-5-(4-methylpent-1-en-1-yl)phenyl)propanal as acolorless liquid. ¹H NMR (CDCl₃): δ=9.95-9.82 (m, 1H, CHO), 7.20-7.04(m, 3H, Ar—H), 6.30 (d, J=15.8 Hz, 1 H, Ar—CH═CH—), 6.23-6.09 (m, 1 H,Ar—CH═CH—CH₂—), 2.91 (t, J=7.6 Hz, 2 H, Ar—CH₂—CH₂—CHO), 2.80-2.70 (m,2H, Ar—CH₂—CH₂—CHO), 2.28 (s, 3 H, Ar—CH₃), 2.08 (dd, J=6.7 Hz, 2 H,(CH₃)₂CH—CH₂—CH═), 1.75-1.69 (m, 1 H, (CH₃)₂CH—), 0.93 (d, J=6.7 Hz, 6H, 2CH₃). ¹³C NMR (CDCl₃): δ=201.6 (d), 138.5 (s), 136.0 (s), 134.4 (s),130.6 (d), 130.5 (d), 129.2 (d), 126.3 (d), 123.9 (d), 44.1 (d), 42.4(t), 28.6 (d), 25.5 (t), 22.4 (q), 19.0 (q). MS: m/z (%)=230 (22) [M⁺],187 (3), 169 (5), 156 (5), 143 (100), 128 (21), 115 (8), 105 (1), 91(4), 77 (3), 65 (2), 51 (1), 41 (3).

J) 3-(2-Methyl-5-(4-methylpentyl)phenyl)propanal

To a 100 mL round-bottomed flask was added(E)-3-(2-methyl-5-(4-methylpent-1-en-1-yl)phenyl)propanal (0.50 g, 2.2mmol) in ethyl acetate (10 ml) to give a colorless solution. Thesolution was de-gassed and purged with argon. Palladium on charcoal(0.05 g, Pd content of 10%) was added. The reaction was stirred underhydrogen atmosphere for 2 h until completion of the conversion(confirmed by GC). The reaction mixture was filtered through a small padof silica gel and the solid was rinsed with ethyl acetate. The filtratewas collected and concentrated. The residue obtained was distilled byKugelrohr to give 0.45 g of3-(2-methyl-5-(4-methylpentyl)phenyl)propanal as a colorless liquid.Odor description: green, anisic, aldehydic, fatty. ¹H NMR (CDCl₃):δ=9.86-9.83 (m, 1H, CHO), 7.06 (d, J=8.0 Hz, 1H, Ar—H), 6.95 (d, J=8.0Hz, 1H, Ar—H), 6.94 (s, 1H, Ar—H), 2.92 (t, J=7.7 Hz, 2 H,Ar—CH₂—CH₂—CHO), 2.73 (t, J=7.8 Hz, 2 H, Ar—CH₂—CH₂—CHO), 2.52 (t, J=7.8Hz, 2 H, Ar—CH₂—CH₂—CH₂), 2.27 (s, 3 H, Ar—CH₃), 1.63-1.52 (m, 3 H,(CH₃)₂CH—CH₂—CH₂—), 1.26-1.16 (m, 2 H, Ar—CH₂—CH₂—CH₂—), 0.87 (d, J=6.6Hz, 6 H, 2 CH₃). ¹³C NMR (CDCl₃): δ=201.8 (d), 140.9 (s), 138.2 (s),132.9 (s), 130.3 (d), 128.7 (d), 126.4 (d), 44.2 (t), 38.7 (t), 35.8(t), 29.5 (t), 27.9 (d), 25.5 (t), 22.6 (q), 18.9 (q). MS: m/z (%)=232(50) [M⁺], 214 (64), 204 (4), 188 (14), 176 (23), 161 (42), 143 (57),129 (32), 119 (100), 105 (75), 91 (40), 77 (7), 65 (5), 55 (7), 43 (18).

The following compounds were prepared according to the sequencedescribed in Example 11.

EXAMPLE 12

3-(5-Isobutyl-2-methylphenyl)propanal

Odor: aldehydic, floral, pungent

¹H NMR (CDCl₃): δ=9.86-9.83 (m, 1H, CHO), 7.05 (d, J=8.0 Hz, 1 H, Ar—H),6.91 (d, J=8.0 Hz, 1 H, Ar—H), 6.90 (s, 1 H, Ar—H), 2.92 (t, J=7.6 Hz, 2H, Ar—CH₂—CH₂—CHO), 2.73 (t, J=7.6 Hz, 2 H, Ar—CH₂—CH₂—CHO), 2.41 (d,J=7.1 Hz, 2 H, Ar—CH₂—CH(CH₃)₂), 2.28 (s, 3 H, Ar—CH₃), 1.88-1.74 (m,1H, (CH₃)₂CH—), 0.88 (d, J=6.6 Hz, 6 H, 2 CH₃). ¹³C NMR (CDCl₃): δ=201.8(d), 139.6 (s), 137.9 (s), 132.9 (s), 130.1 (d), 129.4 (d), 127.2 (d),45.0 (t), 44.2 (t), 30.2 (d), 25.5 (t), 22.4 (q), 18.8 (q). MS: m/z(%)=204 (37) [M⁺], 186 (32), 161 (83), 143 (62), 129 (17), 119 (100),105 (36), 91 (32), 77 (11), 65 (5), 55 (4), 41 (9).

EXAMPLE 13

3-(5-Isopentyl-2-methylphenyl)propanal

Odor: floral, aldehydic, watery, metallic

¹H NMR (CDCl₃): δ=9.86-9.82 (m, 1H, CHO), 7.05 (d, J=8.1 Hz, 1 H, Ar—H),6.95 (d, J=8.1 Hz, 1 H, Ar—H), 6.94 (s, 1 H, Ar—H), 2.91 (t, J=7.6 Hz, 2H, Ar—CH₂—CH₂—CHO), 2.73 (t, J=7.6 Hz, 2 H, Ar—CH₂—CH₂—CHO), 2.54 (t,J=8.0 Hz, 2 H, Ar—CH₂—CH₂—CH(CH₃)₂), 2.27 (s, 3 H, Ar—CH₃), 1.64-1.52(m, 1H, (CH₃)₂CH—), 1.51-1.41 (m, 2 H, Ar—CH₂—CH₂CH(CH₃)₂), 0.92 (d,J=6.4 Hz, 6 H, 2 CH₃). ¹³C NMR (CDCl₃): δ=201.8 (d), 141.0 (s), 138.2(s), 132.9 (s), 130.3 (d), 128.7 (d), 126.4 (d), 44.2 (t), 41.0 (t),33.4 (t), 27.7 (d), 25.1 (t), 22.6 (q), 18.9 (q). MS: m/z (%)=218 (44)[M⁺], 200 (20), 175 (5), 161 (27), 144 (80), 131 (23), 118 (100), 105(48), 91 (41), 77 (12), 65 (5), 55 (5), 41 (14).

EXAMPLE 14

3-(5-Isopentyl-2-methylphenyl)-2-methylpropanal

Odor: watery, aldehydic

5 ¹H NMR (CDCl₃): δ=9.75-9.69 (m, 1H, CHO), 7.06 (d, J=7.6 Hz, 1 H,Ar—H), 6.95 (d, J=8.0 Hz, 1 H, Ar—H), 6.92 (s, 1 H, Ar—H), 3.06 (dd,J=5.8 Hz, 13.6 Hz, 2 H, Ar—CH₂—CH(CH₃)—CHO), 2.69-2.58 (m, 1H, CH—CHO),2.54 (t, J=7.4 Hz, 2 H, Ar—CH₂—CH₂—CH(CH₃)₂), 2.27 (s, 3 H, Ar—CH₃),1.65-1.51 (m, 1H, (CH₃)₂CH—), 1.50-1.41 (m, 2 H, Ar—CH₂—CH—CH(CH₃)₂),1.11 (d, J=6.9 Hz, 3 H, CH₃), 0.92 (d, J=6.4 Hz, 6 H, 2 CH₃). ¹³C NMR(CDCl₃): β=204.5 (d), 140.7 (s), 136.9 (s), 133.1 (s), 130.4 (d), 129.8(d), 126.5 (d), 46.9 (d), 41.0 (t), 33.9 (t), 33.3 (t), 27.7 (d), 22.6(q), 19.1 (q), 13.5 (q). MS: m/z (%)=232 (25) [M⁺], 214 (21), 199 (5),175 (34), 158 (33), 143 (14), 131 (15), 119 (100), 105 (38), 91 (25), 77(8), 65 (4), 55 (3), 41 (10).

EXAMPLE 15

3-(5-Isobutyl-2-methylphenyl)-2-methylpropanal

Odor: green, fatty, aldehydic, bisabolene-like

¹H NMR (CDCl₃): δ=9.73-9.70 (m, 1H, CHO), 7.06 (d, J=7.7 Hz, 1 H, Ar—H),6.91 (d, J=7.7 Hz, 1 H, Ar—H), 6.88 (s, 1 H, Ar—H), 3.11-3.03 (m, 1 H,Ar—CH₂—CH(CH₃)—CHO), 2.70-2.49 (m, 2 H, Ar—CH₂—CH(CH₃)—CHO), 2.41 (d,J=7.1 Hz, 2 H, Ar—CH₂—CH(CH₃)₂), 2.28 (s, 3 H, Ar—CH₃), 1.86-1.77 (m,1H, (CH₃)₂CH—), 1.10 (d, J=6.6 Hz, 3 H, CH₃), 0.88 (d, J=6.6 Hz, 6H, 2CH₃). ¹³C NMR (CDCl₃): δ=204.6 (d), 139.3 (s), 136.6 (s), 133.2 (s),130.6 (d), 130.3 (d), 127.3 (d), 46.9 (d), 45.0 (t), 33.9 (t), 30.3 (d),22.4 (q), 22.3 (q), 19.0 (q), 13.4 (q). MS: m/z (%)=218 (35) [M⁺], 200(47), 185 (7), 175 (46), 161 (86), 147 (29), 129 (15), 119 (100), 105(72), 91 (32), 77 (12), 67 (4), 57 (7), 41 (13).

EXAMPLE 16

2-Methyl-3-(2-methyl-5-(4-methylpentyl)phenyl)propanal

Odor: watery, aldehydic, metallic, sharp, citrus, mandarin

¹H NMR (CDCl₃): δ=9.73-9.70 (m, 1H, CHO), 7.06 (d, J=7.6 Hz, 1H, Ar—H),6.95 (d, J=7.6 Hz, 1H, Ar—H), 6.92 (s, 1H, Ar—H), 3.11-3.03 (m, 1 H,Ar—CH₂—CH(CH₃)—CHO), 2.66-2.48 (m, 4 H), 2.27 (s, 3 H, Ar—CH₃),1.63-1.48 (m, 3 H, (CH₃)₂CH—CH₂—CH₂—), 1.25-1.16 (m, 2 H,Ar—CH₂—CH₂—CH₂—), 1.10 (d, J=6.9 Hz, 3 H, CH₃), 0.86 (d, J=6.6 Hz, 6 H,2 CH₃). ¹³C NMR (CDCl₃): δ=204.4 (d), 140.6 (s), 136.9 (s), 133.2 (s),130.4 (d), 129.9 (d), 126.6 (d), 46.9 (d), 38.7 (t), 35.8 (t), 33.9 (t),29.5 (t), 27.9 (d), 22.6 (q), 19.1 (q), 13.4 (q). MS: m/z (%)=246 (38)[M⁺], 228 (73), 213 (13), 203 (5), 189 (53), 176 (31), 157 (32), 147(32), 131 (22), 119 (98), 105 (100), 91 (37), 77 (12), 65 (5), 55 (9),43 (24).

EXAMPLE 17

3-(2-Methyl-5-(4-methylpentyl)phenyl)butanal

Odor: weak, green, watery, floral

¹H NMR (CDCl₃): δ=9.73-9.69 (m, 1H, CHO), 7.05 (d, J=7.7 Hz, 1H, Ar—H),6.98 (s, 1H, Ar—H), 6.93 (d, J=7.7 Hz, 1H, Ar—H), 3.63-3.51 (m, 1 H,Ar—C/CH₃)—CH₂—CHO), 2.79-2.60 (m, 2 H, CH—CH₂—CHO), 2.53 (t, J=7.8 Hz, 2H, Ar—CH₂—), 2.32 (s, 3 H, Ar—CH₃), 1.63-1.49 (m, 3 H,(CH₃)₂CH—CH₂—CH₂—), 1.27 (d, J=6.9 Hz, 3 H, CH₃), 1.26-1.16 (m, 2 H,Ar—CH₂—CH₂—CH₂—), 0.87 (d, J=6.6 Hz, 6 H, 2 CH₃). ¹³C NMR (CDCl₃):δ=204.4 (d), 143.3 (s), 141.0 (s), 132.2 (d), 130.5 (d), 126.2 (d),125.4 (d), 51.2 (d), 38.7 (t), 36.0 (t), 29.5 (t), 29.3 (d), 27.9 (d),22.6 (q), 21.6 (q), 19.0 (q). MS: m/z (%)=246 (89) [M⁺], 228 (42), 213(14), 203 (100), 189 (14), 175 (31), 161 (34), 143 (26), 133 (90), 119(55), 105 (78), 91 (35), 77 (11), 65 (5), 55 (9), 43 (31).

EXAMPLE 18

In this floral perfume formulation 3-(4-isobutyl-2-methylphenyl)propanalincreases the floral signature and makes this chypre fresher with a nicefloral vibration, emphasizing the softness of the woods whilemaintaining the fruity spicy tonality

ETHYL PHENYL ALCOHOL 60-12-8 20.00 ALD C 11 UNDECYLENIQUE at 10% in BB9.00 AMBERMAX 10%/TEC 3.00 BENZYL BENZOATE 120-51-4 93.00 BERGAMOTE ESSITALIE ORPUR 8007-75-8 75.00 CASHMERAN 33704-61-9 9.00 CHENE EXTRAITCO2/ETHANOL 8.00 CITRON ESS ITALIE SFUMATRICE ORPUR 8008-56-8 45.00DIHYDRO ISOJASMONATE METHYLE 37172-53-5 100.00 GALBANUM ESS CONCENTREE10% in DPG 25.00 GERANIOL 980 106-24-1 15.00 GIVESCONE 57934-97-1 100.00GRAPEFRUIT ESS COSMOS 8016-20-4 30.00 JASMIN ABS COMMUNELLE 8022-96-610.00 JAVANOL 198404-98-7 2.00 KOHINOOL 862107-86-6 20.00 NONADIENOL-2,610%/TEC at 1% in BB 15.00 OENANTHATE ALLYLE at 10% in BB 8.00 PATCHOULIESS FRACTION INDONESIE 8014-09-3 20.00 ORPUR PECHE PURE 104-67-6 3.00PEPPERWOOD 67643-70-3 55.00 SYLKOLIDE 676532-44-8 70.00 VERTOFIX COEUR32388-55-9 120.00 3-(4-ISOBUTYL-2- 45.00 METHYLPHENYL)PROPANAL 900.00

EXAMPLE 19

In vitro metabolism study. A comparison of compounds of the presentinvention and Lilial™.

Cryopreserved hepatocytes from male rats (Sprague Dawley;Lifetechnologies) were defrozen, washed in Cryopreserved HepatocytesRecovery Medium (CHRM; Lifetechnologies) and suspended in Williams EMedium (WEM; Lifetechnologies). Lilial™, or the compounds of the presentinvention (final concentration: 100 μM) were added to the cells (1×10⁶viable cells/ml) and suspensions were incubated up to 4 hours at 37° C.on a shaker in duplicate. Metabolism of testosterone was monitored aspositive control. Decrease of the test compounds and formation of thecorresponding benzoic acid derivative was determined by GC-MS analysisof methyl esters formed after derivatisation with trimethylsilyldiazomethane (Sigma-Aldrich) in methanol. The test compounds react withdiazomethane yielding a methyl ketone which was used for thequantification of Lilial™ and the compound of formula (I). Metabolismwas stopped with ice cold 1 M HCl, samples were extracted withtert-butyl methyl ether (MTBE) and analysed by GC-MS. Incubationscontaining testosterone as control were also stopped with ice cold 1 MHCl, centrifuged to separate the cells, filtrated and the decrease oftestosterone analysed by LC-MS. To quantify decrease of the testsubstances and formation of benzoic acid metabolites, calibration curvesof reference materials (Lilial™ and the compounds of the presentinvention, tert-butyl benzoic acid (Fluka) was prepared in hepatocyteincubation medium and analysed like the hepatocyte samples.

A rapid decrease of testosterone as positive control was observedindicating that the hepatocytes were metabolically active. The compoundsof the present invention and Lilial™ were metabolised rapidly in rathepatocytes and no residual compound except for 2% with one compound wasmeasured after 4 h. Whereas tert-butyl benzoic acid was detected asmetabolite of Lilial™ (3.4-3.9 μM) no benzoic acid derivatives wereformed from compounds of the present invention (Table 1). Limit ofdetection was <1 μM.

Table 1 (below), shows the concentrations of Lilial™ and compounds ofthe present invention as well as corresponding benzoic acid metabolitesin rat hepatocytes within 4 hours incubation. Initial test concentrationat 0 hours incubation was 100 μM.

It is clear from the data presented in Table 1 that the orthosubstituent at the benzene ring of the compounds of the presentinvention prevents the formation of the corresponding benzoic acidderivative in vitro. Since benzoic acid derivatives such as tert-butylbenzoic acid from Lilial™ cause reproductive toxicity in male rats,these toxic effects in male rats are prevented by the ortho-substituentof the compounds of the present invention.

Residual concentration Benzoic acid Concentration Test compound (μM)derivative (μM)

0

3.5-3.9 μM

0

not found

0

not found

0

not found

0

not found

0

not found

2.4 μM

not found

The invention claimed is:
 1. An aryl-substituted alkanal compound havinga molecular weight of less than 300 g/mol and which bears a substituenton the aryl ring ortho to a substituent bearing the aldehydefunctionality, and is represented by Formula 1

wherein, R₁, R₂, R₃, R₆ and R₇ each independently may represent H ormethyl; R₄ is H, or when R₅ is H, R₄ is a C₁-C₇ branched or linear,saturated or unsaturated, unsubstituted or substituted, optionally withcyclopropyl groups, alkyl radical; R₅ is H, or when R₄ is H, R₅ is aC₁-C₇ branched or linear, saturated or unsaturated, unsubstituted orsubstituted, optionally with cyclopropyl groups, alkyl radical; or R₄and R₅ together with the carbon atoms to which they are attached, form asubstituted or unsubstitued 5-membered ring; n=0, 1, 2; the dotted linerepresents an optional single bond, with the proviso that when thedotted line represents a single bond R₄ or R₅ are sec-butyl, iso-butylor a C₅-C₇ branched or linear, saturated or unsaturated alkyl residue;and wherein the compounds are not selected from5-(tert-butyl)-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-(tert-butyl)-2,3-dihydro-1H-indene-2-carbaldehyde,5-isopropyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-isopropyl-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-ethyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-ethyl-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,5-methyl-2,3-dihydro-1H-indene-2-carbaldehyde,2,5-dimethyl-2,3-dihydro-1 H-indene-2-carbaldehyde,3-(5-(tert-butyl)-2-methylphenyl)propanal,3-(5-(tert-butyl)-2-methylphenyl)-2-methyl propanal,3-(5-isopropyl-2-methylphenyl)propanal,3-(5-isopropyl-2-methylphenyl)-2-methylpropanal,3-(5-ethyl-2-methylphenyl)propanal,3-(5-ethyl-2-methylphenyl)-2-methylpropanal,3-(4-(tert-butyl)-2-methylphenyl)propanal,3-(4-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(4-isopropyl-2-methylphenyl)propanal,3-(4-isopropyl-2-methylphenyl)-2-methylpropanal,3-(4-ethyl-2-methylphenyl)propanal,3-(4-ethyl-2-methylphenyl)-2-methylpropanal or a compound of formula 3

wherein R₁ through R₅ is independently H or methyl.
 2. A method ofutilizing the compound according to claim 1 as a perfume ingredientexhibiting muguet odour characteristics to a personal care or householdcare composition comprising the step of adding to said composition thecompound or a perfume composition containing said compound.
 3. A perfumecomposition comprising the compound as defined in claim 1, whichcomposition is free of any aryl-substituted alkanal, optionally free ofany aryl-substituted propanal, odourants that are unsubstituted on thearyl ring at a position ortho to the substituent bearing the aldehydefunctionality, and optionally free of3-(4-tert-butylphenyl)-2-methypropanal.
 4. A personal care or householdcare composition perfumed with an aryl-substituted alkanal compoundaccording to claim
 1. 5. A personal care or household care compositionaccording to claim 4 containing enzymes.
 6. The personal or householdcare composition according to claim 5 characterised in that it is atextile treatment product.
 7. The personal or household care compositionaccording to claim 5 characterised in that it is a detergentcomposition.
 8. A method of imparting muguet odour characteristics to afine fragrance or consumer product comprising the step of adding theretoan aryl-substituted alkanal compound defined in claim 1, and selectivelyexcluding from said fine fragrance or consumer product anyaryl-substituted alkanal compounds, which are unsubstituted on the ringat the position ortho to the substituent containing aldehydefunctionality, said selective addition or exclusion being based on thesusceptibility of said compounds to enzymatically-mediated degradationto their benzoic acid derivatives when incubated with hepatocytesisolated from rats, said compounds being suitable for addition on thebasis that they do not degrade to their benzoic acid derivatives,whereas said compounds being excluded on the basis that they do degradeto their benzoic acid derivatives.
 9. An aryl-substituted alkanalcompound having a molecular weight of less than 300 g/mol and whichbears a substituent on the aryl ring ortho to a substituent bearing thealdehyde functionality, represented by Formula 2

wherein R₁, R₂, R₃, and R₆ each independently may represent H or methyl;R4 is H, or when R₅ is H, R₄ is a C₁-C₇ branched or linear, saturated orunsaturated, unsubstituted or substituted, optionally with cyclopropylgroups, alkyl radical; R₅ is H, or when R₄ is H, R₅ is a C₁-C₇ branchedor linear, saturated or unsaturated, unsubstituted or substituted,optionally with cyclopropyl groups, alkyl radical; or R₄ and R₅ togetherwith the carbon atoms to which they are attached, form a substituted orunsubstitued 5-membered ring; and wherein the compounds are not3-(5-(tert-butyl)-2-methylphenyl)propanal,3-(5-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(5-isopropyl-2-methylphenyl)propanal,3-(5-isopropyl-2-methylphenyl)-2-methylpropanal,3-(5-ethyl-2-methylphenyl)propanal,3-(5-ethyl-2-methylphenyl)-2-methylpropanal,3-(4-(tert-butyl)-2-methylphenyl)propanal,3-(4-(tert-butyl)-2-methylphenyl)-2-methylpropanal,3-(4-isopropyl-2-methylphenyl)propanal,3-(4-isopropyl-2-methylphenyl)-2-methylpropanal,3-(4-ethyl.-2-methylphenyl)propanal,3-(4-ethyl-2-methylphenyl)-2-methylpropanal, or a compound of formula 3

wherein R₁ through R₅ is independently H or methyl.
 10. A method ofutilizing the compound according to claim 9 as a perfume ingredientexhibiting muguet odour characteristics to a personal care or householdcare composition comprising the step of adding to said composition thecompound or a perfume composition containing said compound.
 11. Aperfume composition comprising the compound as defined in claim 9, whichcomposition is free of any aryl-substituted alkanal, optionally free ofany aryl-substituted propanal, odourants that are unsubstituted on thearyl ring at a position ortho to the substituent bearing the aldehydefunctionality, and optionally free of3-(4-tert-butylphenyl)-2-methylpropanal.
 12. A personal care orhousehold care composition perfumed with an aryl-substituted alkanalcompound according to claim
 9. 13. A personal care or household carecomposition according to claim 12 containing enzymes.
 14. The personalor household care composition according to claim 12 characterised inthat it is a textile treatment product.
 15. The personal or householdcare composition according to claim 12 characterised in that it is adetergent composition.
 16. A method of imparting muguet odourcharacteristics to a fine fragrance or consumer product comprising thestep of adding thereto an aryl-substituted alkanal compound defined inclaim 9, and selectively excluding from said fine fragrance or consumerproduct any aryl-substituted alkanal compounds, which are unsubstitutedon the ring at the position ortho to the substituent containing aldehydefunctionality, said selective addition or exclusion being based on thesusceptibility of said compounds to enzymatically-mediated degradationto their benzoic acid derivatives when incubated with hepatocytesisolated from rats, said compounds being suitable for addition on thebasis that they do not degrade to their benzoic acid derivatives,whereas said compounds being excluded on the basis that they do degradeto their benzoic acid derivatives.